CA1205491A - Process for the preparation of 4- chlorobenzenesulfonyl chloride - Google Patents
Process for the preparation of 4- chlorobenzenesulfonyl chlorideInfo
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- CA1205491A CA1205491A CA000422389A CA422389A CA1205491A CA 1205491 A CA1205491 A CA 1205491A CA 000422389 A CA000422389 A CA 000422389A CA 422389 A CA422389 A CA 422389A CA 1205491 A CA1205491 A CA 1205491A
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- chlorobenzene
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Abstract
SPECIFICATION
Title of the Invention Process for the Preparation of 4-Chlorobenzenesulfonyl Chloride Abstract of the Disclosure A process for the preparation of 4-chloro-benzenesulfonyl chloride wherein chlorobenzene is reacted with chlorosulfonic acid in a halogenated aliphatic hydrocarbon in the presence of an alkali metal salt of a mineral acid and/or an ammonium salt of a mineral acid. After washing the resulting reaction mixture with water and separating the halogenated aliphatic hydrocarbon layer, water is distilled off, together with -the halogenated aliphatic hydrocarbon to obtain 4-chlorobenzenesulfonyl chloride in an anhydrous state. The anhydrous 4-chlorobenzene-sulfonyl chloride thus obtained can be converted into 4,4'-dichlorodiphenyl sulfone by reacting it with chlorobenzene in the presence of a catalytic amount of ferric chloride.
Title of the Invention Process for the Preparation of 4-Chlorobenzenesulfonyl Chloride Abstract of the Disclosure A process for the preparation of 4-chloro-benzenesulfonyl chloride wherein chlorobenzene is reacted with chlorosulfonic acid in a halogenated aliphatic hydrocarbon in the presence of an alkali metal salt of a mineral acid and/or an ammonium salt of a mineral acid. After washing the resulting reaction mixture with water and separating the halogenated aliphatic hydrocarbon layer, water is distilled off, together with -the halogenated aliphatic hydrocarbon to obtain 4-chlorobenzenesulfonyl chloride in an anhydrous state. The anhydrous 4-chlorobenzene-sulfonyl chloride thus obtained can be converted into 4,4'-dichlorodiphenyl sulfone by reacting it with chlorobenzene in the presence of a catalytic amount of ferric chloride.
Description
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Background of the Invention 1. Field of the Invention This invention relates to a novel and improved process for the preparation of 4-chloro-benzenesulfonyl chloride. More specifically, itrelates to a process for the preparation of 4-chlorobenzenesulfonyl chloride in which chlorobenzene is reacted with chlorosulfonic acid in a halogenated aliphatic hydrocarbon solvent in the presence of an alkali metal salt of a mineral acid and/or an ammonium salt of a mineral acid~
Background of the Invention 1. Field of the Invention This invention relates to a novel and improved process for the preparation of 4-chloro-benzenesulfonyl chloride. More specifically, itrelates to a process for the preparation of 4-chlorobenzenesulfonyl chloride in which chlorobenzene is reacted with chlorosulfonic acid in a halogenated aliphatic hydrocarbon solvent in the presence of an alkali metal salt of a mineral acid and/or an ammonium salt of a mineral acid~
2. Description of the Prior Art 4-Chlorobenzenesulfonyl chloride is an important raw material for the preparation of 4,4'-dichlorodiphenyl sulfone that is a monomer used .i.n the manufacture of polysulfone resins having excellent thermal resistance. Besides, this sub-stance is useful as a raw material for the manufacture of various drugs, agricultural chemicals, and dyes.
It is well known that 4-chlorobenzene-sulfonyl chloride can be prepared by reacting chlorobenzene with a stoichiometrically excessive amount of chlorosulfonic acid. For example, 4-chlorobenzenesulfonyl chloride has ~een prepared in ~L2~115~
a 72-73% yield by reacting 1 mole of chlorobenzene with 3 moles of chlorosulfonic acid, and it has been prepared in an 80% yield by using 8 moles of chlorosulfonic acid [A. M. Grigorovskiy et al., Zhur.
Priklad. Khim., 28, 616-21(1955): Chem. Abstr., 50, 3279(1956)]. Moreover, the desired product has been prepared in a 70% yield by reacting 1 mole of chlorobenz~ne with 4 moles o:E chlorosulfonic acid at a temperature of 60C [J. M. Dumont et al., Bull.
Soc. ~him. France, 1962, 1231-18; Chem. Abstr., 57, 9717(1962)]. Thus, a large excess of chlorosulfonic acid is required to prepare 4-chlorobenzenesulfonyl chloride in an 80% or higher yield by the reaction of chlorobenzene with chlorosulfonic acid~ Accord-ingly, if this method is put into industrial practice, there will be a great disadvantage from the viewpoint of economy and, in particular, environmental protectlon.
In the reaction of an aromatic compound with chlorosulfonic acid, an aromatic sulfonic acid and a diaryl sulfone are formed as by-products, along with the desired aromatic sulfonyl chloride For example, when 1 mole of chlorobenzene is reacted with 3 moles of chlorosulfonic acid, 4,4'-dichloro-diphenyl sulfone is formed as a by-product in a 12~
. .
.
126P54~9~
yield, along with 4-chlorobenzenesulfonyl chloride (61% yield) [F. Ullmann et al., Ber., 40, 641(1907~].
It is also stated in the aforementioned article by A. M. Grigorovskiy et al. that, when chlorosulfonic acid is used at a molar ratio of 3, 4-chlorobenzene-sulfonic acid (20% yield) and 4,4'-dichlorodiphenyl sulfone (8% yield) are formed as by-products. It is generally said that chloroform and carbon tetra-chloride are useful for the purpose of suppressing side reactions in the reaction of an aromatic compound with chlorosulfonic acid [New Lectures on Experi~ental Chemistry, Vol. 14, "Syntheses and Reactions of Organic Compounds (III)", pp. 1787-1788, ~aruzen (1978)]. When chlorobenzene is reacted with chlorosulfonic aci.d in such a solvent (for exa.mple, when 1 mole of chlorobenzene is reacted with 3 moles of chlorosulfonic acid in chloroform), no by-product worthy of mention is formed, but the yield of 4-chlorobe~zenesulfonyl chloride is as low as 74.6%
20 (Japanese Patent Publication No. 19457/'67).
In order to enhance the yield of 4-chloro-benzenesulfonyI chloride, there is a well-known method in which chlorosul.fonic acid is reacted with sodium 4-chlorobenzenesulfonate. As described in the aforementioned article by Grigorovskiy et al., 1~5~
this method enables the desired product to be prepared in an 80% yield. It is also well known that this method can be carried out in an organic sol~en-t. Specifically, there has been proposed a process in which 4-chlorobenzenesulfonyl chloride is prepared in a yield of as high as 89% by suspending dried sodium 4-chlorobenzenesulfonate in chloroform and then reacting it with chlorosulfonic acid in an amount of 2 moles per mole of the sodium 4-chloro-benzenesulfonate [M. Kulka, J. Am. Chem. Soc., 72,1215(1950)~.
Although the amount of chlorosulfonic acid used is small and the yield is satisfactorily high, this process has the disadvantage that sodium 4-chlorobenzenesulfonate serving as one of the raw materials must be isolated and used in an anhydrous state. Thus, this process is not regarded as advantageous from an industrial point of view because it cannot be carried out economically.
Judging from these existing conditions of the art, it is a vital industrial problem concerning the reaction of chlorobenzene with chlorosulfonic acid to decrease the amount of chlorosulfonic acid used, suppress the formation of by-products, and obtain 4-chlorobenzenesulfonyl chloride in high yield.
- It is widely known that 4,4l-dichloro-diphenyl sulfone can be prepared by the Friedel-Crafts reaction in which 4-chlorobenzenesulfonyl chloride is reacted with chlorobenzene by using anhydrous ferric chloride as the catalyst [see, for e~ample, U.S. Patent 3,334,146(1967) and the like3.
In carrying out this process, however, it lS essen-tial to use 4-chlorobenzenesulfonyl chloride in an anhydrous s~ate.
As stated before, 4-chlorobenzenesulfonyl ehloride ean be prepared by reacting chlorobenzene with a stoiehiometrically exeessive amount of chlorosulfonic acid and then pouring the reaction mixture into ice water~ In this process, 4,4'-dichlorodiphenyl sulfone is formed as a by-product.
Accordingly, when the reaetion mixture containing 4-ehlorobenzenesulfonyl ehloride and 4,4'-dichloro-diphenyl sulfone is poured into ice water and the resulting mixture is heated to 90~C, 4-chloro-benzenesulfonyl chloride is hydrolyzed to 4-chlorobenzenesulfonic acld. Accordingly~ this process also serves to prepare 4,4'-dichlorodiphenyl sulfone by isolating the 4-chlorobenzenesulfonic acid so formed [U.S. Patent 2,860,168(1958)].
As is obvious from this fact, 4-ehloro-benzenesulfonyl ehloride is easily hydrolyzed to ~s~
4-chlorobenzenesulfonic acid. Accordingly, if it is desired to subject 4-chlorobenzenesulfonyl chloride - obtained as above to the Friedel-Crafts reaction with chlorobenzene, it must be dehydrated by, after completion of the reaction, pouring the reaction mixture into ice water, separating the product by filtration, and then drying it under reduced pressure.
However, in preparing 4-chlorobenzenesulfonyl chloride by the reaction of chlorobenzene with chlorosulfonic acid, a process including the steps of pouring the reaction mixture into ice water, separating the product by filtration, and drying to dehydra~e it cannot be regarded as an industrially satisfactory one from the viewpoint of manufacturing operation and economy.
In view of these facts, it is another vital industrial problem concerning the reaction of chloro-benæene with chlorosulfonic acid to decrease the amount of chlorosulfonic acid used, suppress the formation of by-products, and obtain anhydrous 4-chlorobenzenesulfonyl chloride in high yield.
Furthermore, a number of processes are conventionally known in which chlorobenzene used as a starting material is chlorosulfonylated and then converted into 4,4-dichlorodiphenyl sulfone without 5~
isolatlng the intermediate product. They include, for example, (1) a process in which chlorobenzene is reacted wi-th sulfur trioxide to form 4-chlorobenzenesulfonic acid, a chlorinating agent or thionyl chloride is allowed to act thereon, and the 4-chloro-benzenesulfonyl chloride so formed is condensed with chlorobenzene (Japan~se Pa-tent Publication ~o. $386/'81);
0 (2) a process in which chlorobenzene is reacted with both sulfur trioxide and thionyl chloride, and the 4-chlorobenzenesulfonyl chloride so formed is condensed with chlorobenzene [U.S.S.R.
568,637, Chem. Abstr., 87, 167728 b(l977)]; and 5 (3) a process in which chlorobenzene is reacted with chlorosu~lfonic acid to form 4-chlorobenzene-sulfonic acid, phosphorus oxychloride is reacted -therewith, and the 4-chlorobenzenesulfonyl chloride so formed is condensed with chloro-benzene [U.S. Patent 3,125,604(196~)].
In these processes, unexpensive sulfonating agents such as sulfur trioxide and chlorosulfonic acid are used. However, the chlorinating agents used therein, i.e. thionyl chloride and phosphorus 5 oxychloride, are relatively expensive and, therefore, the excess chlorinatiny agent is recovered after completion of the reaction. Accordingly, if these processes are put into industrial practice, there will be the disadvantages that provision for the recovery of the chlorinating agent must be made and the reuse of the recovered chlorinating agent is relatively difficult because it is easily decomposable. Thus, as a means for the industrial production of 4,4'-dichlorodlphenyl sulfone, none of the above-described processes are considered to be satisfactory from the viewpoint of both manufacturing operation and economy.
On the other hand, it is widely known that 4-chlorobenzenesulfonyl chloride is formed by reacting chlorobenzene with a stoichiometric amount of chlorosulfonic acid. However, if it i5 intended to form 4-chlorobenzenesulfonyl chloride according to this method and then subject it to the Friedel-Crafts reaction without isolating it, consideration must be given to the theoretical amount of sulfuric acid formed as a by-product. More specifically, it is necessary to prepare anhydrou~s 4-chlorobenzenesulfonyl chloride by, after completion of the reaction, pouring the reaction mixture into ice water and passing the resulting mixture through filtering, water-washing and drying steps, and then subjecting this inter-mediate product to condensation reaction with 5~
chlorobenzene. Thus, this method is not advantageous from an industrial point of view.
Nevertheless, the method using chloro-benzene and chlorosulfonic acid as the raw materials has the advantage that chlorosulfonic acid is easy to handle and industrially inexpensive. Accordingly, it is desirable in this ~ield of industry to prepare 4,4'-dichlorodiphenyl sulfone by reacting chlorobenzene with chlorosulfonic acid to form 4-chlorobenezene-sulfonyl chloride in an anhydrous state withoutisolating it, and then reacting it with chlorobenzene in the presence of ferric chloride.
Summary of the Invention It is an object of an aspect of the present invention to provide a process for the preparation of 4-chlorobenzenesulfonyl chloride with industrial advantages.
It is an object of an aspect of the present invention to provide a process for the preparation of anhydrous 4-chlorobenzenesulfonyl chloride with industrial advantages.
It is an object of an aspect of the present invention to provide a process for the preparation of 4,4'-dichlorodiphenyl sulfone from chlorobenzene and chlorosulfonic acid via anhydrous 4-chlorobenzene-sulfonyl chloride with industrial advantages.
S~a9~
lOa-Various aspects of the invention are as follows:
A process for the preparation of 4-chlorobenzene-sulfonyl chloride which comprises reacting chlorobenzene with chlorosulfonic acid in at least one organic solvent selected from the group consisting of halogenated aliphatic hydrocarbons in the presence of at least one compound selected from the group consisting of alkali metal salts of mineral acids and ammonium salts of mineral acids, thereby forming 4-chlorobenzenesulfonyl chloride, the chlorosulfonic acid being used in an amount of 2.5 to 4.0 moles per mole of the chlorobenzene.
A process for the preparation of 4,4'-dichlorodi-phenyl sulfone which comprises (a) reacting chlorobenzene with chlorosulfonic acid in a halogena-ted aliphatic hydrocarbon solvent in the presence of an alkali metal salt of a mineral acid and/or an ammonium salt of a mineral acid, the chlorosulfonic acid being used in an amount of 2.5 to 4.0 moles per mole of the chlorobenzene, 0 (b) washing the resulting reaction mix-ture with water, separating the organic solvent layer, and distilling off water, together with the organic solvent, to obtain 4-chlorobenzenesulfonyl chloride in an anhydrous state; and 5 (c) reacting the resulting anhydrous 4-chlorobenzene-sulfonyl chloride with chlorobenzene in the presence of a catalytic amount of ferric chloride.
~2~59~
According to the present invention, 4-chlorobenzenesulfonyl chloride can be prepared in high yield by reacting chlorobenzene with chloro-sulfonic acid in a halogenated aliphatic hydrocarbon solvent in the presence of an alkali metal salt of a mineral acid and/or an an~nonium salt of a mineral acid.
Moreover, anhydrous 4~chlorobenzenesulfonyl chlorid~ can be prepared hy reacting chlorobenzene with chlorosulfonic acid in a halogenated aliphatic hydrocarbon solvent in the presence of an alkali metal salt of a mineral acid and/or an ammonium salt of a mineral acid, washing the resulting reactio~n mixture with water, and then distilling off water, together with the sol.vent, from the separated organic solvent layer.
Furthermore, 4,4'-dichlorodiphenyl sulfone can be obtained by reacting anhydrous 4-chloro-benzenesulfonyl chloride obtained as above with chlorobenzene in the presence of a catalytic amount of ferric chloride.
Detailed Description of the Invention In the process of the present invention, the reaction of chlorobenzene with chlorosulfonic acid is carried out in a halogenated aliphatic ~5~
hydrocarbon solvent in the presence of an alkali metal salt of a mineral acid and/or an ammonium salt of a mineral acid.
The solvents which can be used in the process of the present invention are halogenated aliphatic hydrocarbons and, among others, halogenated lower aliphatic hydrocarbons of 1 or 2 carbon atoms having some or all of the hydrogen replaced with a halogen are preferred. Examples of such halogenated aliphatic hydrocarbons include dichloromethane, chloroform, c~rbon tetrachloride, 1,1 dichloroethane, 1,2-dichloroethane, l,l,l-trichloeroethane, 1,1,2-trichloroethane, 1,1,1,2-tetrachloroethane, 1,1,2,2-tetrachloroethane, 1,2-dichloroethylene, trichloro-ethylene, tetrachloroethylene, pentachloroethylene, hexachloroethylene, and analogous compounds obtained by replacing some or all of the chlorine with other halogensO Although no particular limitation is placed on the amount of solvent used, it is usually 20 used in an amount of 0.5 to 5.0 times, preferably 1.0 to 3.0 times, the weight of the chlorobenzene.
Useful alkali metal salts of mineral acids include the halogenides, sulfates, sulfites, nitrates and phosphates of lithium~ sodium and potassium.
Useful ammonium salts of mineral acids include .
ammonium chloride, ammonium bromide, amrnonium iodide, ammonium sulfate, ammonium sulfite, ammonium nitrate and ammonium phoshphate. If desired, these alkali metals sal-ts of mineral acids and ammonium salts of mineral acids may be used in combination. Such an alkali metal salt of a mineral acid and/or an ammonium salt of a mineral acid are used in an amount of 0.01 to 5 moles, preferably 0.05 to 2 moles, per mole of the chlorobenzene. Although the alkali metal salt and/or ammonium salt may be used in an amount of more than 5 moles per mole of the chlorobenzene, a molar ratio of 5 or less suffices to produce satis-factory effects.
In the process of the present invention, the effects of the solvent and the mineral acid salt(s) ar~ as follows: For example, when 1 mole of chlorobenzene is reacted with 3 moles of chloro-sulfonic acid at 55-60C, 4-chlorobenzenesulfonyl chloride is obtained in a 70% yield and 4,4'-dichlorodiphenyl sulfone is formed in a 9% yield~Moreover, when the aforesaid reaction is carried out using 1,2-dichloroethane as the solvent, the desired produc-t is obtained in a 69% yield and the corre-sponding sulfone is formed in a 10% yield. These results indicate that the solvent has no effect on .
~2~S~
the yield of the desired product and the formation of by-products. ~ext, when 1 mole of chlorobenzene is reac~ed with 3 moles of chlorosulfonic acid a-t the aforesaid temperature in the presence of 0.3 mole of sodium chloride, the desired product is obtained in a 75~ yield, but the sulfone formed as a by-product is decreased. Although the addition of sodium chloride enhances the yield of the desired product only slightly, it is a noteworthy fact that the formation of the sulfone by-product is suppressed.
On the other hand, when the same reaction is carried out accordin~ to -the present invention (that is, 1 mole of chlorobenzene is reacted with 3 moles of chlorosulfonic acid at 55-60C in 1,2-dichloroethane in the presence of 0.3 mole of sodium chloride), the yield of the desired product is markedly increased to 90% and the yield of the by-product is as low as 2.5~. In addition to sodium chloride, alkali metal salts (e.g., lithium, sodium and potassium salts) and ammonium salts of mineral acids (e.g., hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, sulfurous acid, nitric acid, phosphoric acid, etc.) can also produce similar effects.
~hus, by reacting chlorobenzene with chlorosulfonic acid in a halogenated aliphatic .
12t;1 5~
h~drocarbon solvent in the presence of an alkali metal salt of a mineral acid and/or an ammonium salt of a mineral acid, it is possible to prepare the desired product in high yield while suppressing the formation of by-products.
The amounts of chlorobenzene and chloro-sulronic acid used in the process of the present invention are usually such tha-t 2.5 to 4.0 moles, preferably 3.0 to 3.5 moles, of chlorosulfonic acid is provided for each mole of chlorobenzene. The reaction temperature generally ranges from 0 to 100C, the preferred ranye being from 10 to 90~.
No particular limitation is placed on the manner in which the process of the present invention lS is carried out, so long as chlorobenzene can be mixed and reacted ~ith chlorosulfonic acid. Usually, chlorobenzene is added dropwise to a mixture consist-ing of chlorosulfonic acid, an alkali metal salt of a mineral acid and/or an ammonium salt of a mineral acid, and an organic solvent. According to circum-stances, chlorosulfonic acid may be added dropwise to a mixture consisting of chlorobenzene, an alkali metal salt of a mineral acid and/or an ammonium salt of a mineral acid, and an organic solvent. After completion of the addition, the resulting reaction .
.
~f~05~
mixture is stirred at a predetermined temperature for a predetermined reaction time. Then, the reaction mixture is poured into ice water and the organic layer is separated. After the organic layer is washed with water and dried, the solvent is removed therefrom by distillation under reduced pressure to obtain the desired product, or 4-chloro-benzenesulfonyl chloride.
In a preferred embodiment of the present invention, anhydrous 4-chlorobenzenesulfonyl chloride can be obtained. Specifically, after completion of the reaction, the reaction mixture is usually cooled to room temperature and then washed with a sufficient amount of water to remove any by-product sulfuric acid and unreacted chlorosulfonic acid that are present in the reaction mixture. More specifically, the reaction mixture is usually washed by adding water thereto in an amount of, but not limited to t 5 to 6 times the weight of chlorosulfonic acid used.
Thereafter, the organic solvent layer is separated.
The solution so separated is heated under atmospheric pressure to distill off the water contained therein, together with the solvent, and thereby ob-tain 4-chlorobenzenesulfonyl chloride in an anhydrous state.
Although 4-chlorobenzenesulfonyl chloride .. . . I . , .. . ~ .
has the property of being easily hydxolyzed to 4-chlorobenzenesulfonic acid by heating it with water, the present invention enables 4-chloro-benzenesulfonyl chloride to be readily prepared in an anhydrous state.
To this end, the reaction mixture resulting from the reaction of chlorobenzene with chlorosulfonic acid in a halogenated aliphatic hydrocarbon solvent is washed with water to remove any by-product sulfuric acid and unreacted chlorosulfonic acid, and the separated organic solvent is then heated to distill off the water contained therein as the azeotropic mixture with the solvent, whereby 4-chlorobenzene-sul~onyl chloride can be obtained without being hydrolyzed to 4-chlorobenzenesulfonic acid. This is a quite unexpected and surprising fact in view of the prior art and the instability of 4-chlorobenzene~
sulfonyl chloride to water.
According to the present invention, anhydrous 4-chlorobenzenesulfonyl chloride can be prepared in the above-described manner. Therefore, it can be directly reacted with chlorobenzene in the presence of a catalytic amount of ferric chloride to produce 4,4'-dichlorodiphenyl sulfone industrially.
Specifically, chlorobenzene and ferric chloride are added to anhydrous 4-chlorobenzenesulfonyl chloride .5~
obtained as described above. The resulting reaction mixture is stirred at a predetermined temperature for a predetermined reaction time. After completion of the reaction, chlorobenzene is added to the reaction mixture so that its sulfone concentration may be adjusted to approximately 35 to 40%. After being cooled to a temperature of 65 to 70C, the reaction mixture is washed with water at that temperature to remove the ferric chloride. Subsequently, the chlorobenzene is removed by steam distillation to obtain crysta s of 4,4'-dichlorodiphenyl sulfone.
Since the process of the present invention permits 4-chlorobenzenesulfonyl chloride to be prepared in an anhydrous state and in high yield, it can be used directly, i.e. without being isolated, in the production of 4,4'-dichlorodiphenyl sulfone.
This indicates that the process of the present invention has a great industrial value.
In the above-described preparation of 4,4'-dichlorodiphenyl sulfone by reacting anhydrous 4-chlorobenzenesulfonyl chloride with chlorobenzene in the presence of anhydrous ferric chloride, the amount of chlorobenzene used is not critical so long as it is in the range of 1.5 to 2.5 moles per mole of the 4-chlorobenzenesulfonyl chloride. The ferric 5~
chloride is usually used in an amount of 2 to 5 mole % based on the 4-chlorobenzenesulfonyl chloride, and greater amounts produce no additional effect.
The reaction tempera~ure ranges from 140 to 160C.
The progress of the reaction can be readily followed by gas chromatography or high-speed liquid chromato-graphy. Generally, the reaction is completed in 10 to 20 hours.
Thus, according to the present invention, 4,4'-dichlorodiphenyl sulfone can be prepared from chlorobenzene and chlorosulfonic acid with industrial advantages. ~lore specifically, 4,4'-dichlorodiphenyl sulfone can be prepared in high yield by reacting chlorobenzene with chlorosulfonic acid and then reacting the intermediate product with chlorobenzene without isolating it.
The present invention is further illustrated by the following ~xamples.
Example 1 In 250 g of 1,2-dichloroethane were suspended 349 g (3.0 moles) of chlorosulfonic acid and 17.5 g (0.3 mole) of sodium chloride. While this suspension was kept at a temperature of 55-60C, 112.5 g (1.0 mole) of chlorobenzene was added drop-wise thereto over a period of 3 hours. The resulting . .
~. .
reaction mixture was stirred at that temperature for an additional 5 hours, cooled to room temperature, and then poured into 1 liter of ice wa-ter. After this mixture was stirred well, the organic layer was separated therefrom. The same procedure was repeated by using 1 liter of ice water. After drying the separated organic layer, the solvent was removed -therefrom by distillation under reduced pressure to obtain crystals of 4-chlorobenzenesulfonyl chloride.
The results are shown in Table 1.
Examples 2 to 13 The desired product was obtained by repeat-ing the procedure of Example 1, except that the amount of chlorosulfonic acid used, the type and amount of alkali metal salt or ammonium salt used, the type and amount of solvent used, and the reaction temperature were varied as indicated in Table 1. The results are shown in Table 1.
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~ ~ ~
~J ~ O O ~ U~ ~ GO ~ ~ O ~ U) rl ,~::
1 ~ O
~- ~ ~n aJ
~ .
. _.___ ___ I ~
4~ o I ~ ~ 0 O o ~Ho ~ ~ ~ ~`3 0 0~ 0 .~ al o ~-1 rC N ~U O ~ o ~i 0'1 ~1 0 ~1 a~
.~ y ~O O~
~ ____ _____________ _ O I
O O O ul U) U) U) U) D U~ U) ~
~ Ul)Ul) Ul) O O I O O
P~ U~ U) U) U) U) _.._ _ .__ . .
C~
O O O O O O O O
~, ~3 a~
~1 ~
t-d ~1 O ~ ~rl a ~ u~ ~ ~ ~ ~ ~ O ~ a~ ~
~1 ~ f~ Irl h ,~ O h O tlJ
. .C U
' ~3 ri ~a ~a ~ a ~
~ o o o ~ ~ o o o o ~~-----'----~'''~ I o o oo o o U) o ~ot~ U) O OU) U ~I o
It is well known that 4-chlorobenzene-sulfonyl chloride can be prepared by reacting chlorobenzene with a stoichiometrically excessive amount of chlorosulfonic acid. For example, 4-chlorobenzenesulfonyl chloride has ~een prepared in ~L2~115~
a 72-73% yield by reacting 1 mole of chlorobenzene with 3 moles of chlorosulfonic acid, and it has been prepared in an 80% yield by using 8 moles of chlorosulfonic acid [A. M. Grigorovskiy et al., Zhur.
Priklad. Khim., 28, 616-21(1955): Chem. Abstr., 50, 3279(1956)]. Moreover, the desired product has been prepared in a 70% yield by reacting 1 mole of chlorobenz~ne with 4 moles o:E chlorosulfonic acid at a temperature of 60C [J. M. Dumont et al., Bull.
Soc. ~him. France, 1962, 1231-18; Chem. Abstr., 57, 9717(1962)]. Thus, a large excess of chlorosulfonic acid is required to prepare 4-chlorobenzenesulfonyl chloride in an 80% or higher yield by the reaction of chlorobenzene with chlorosulfonic acid~ Accord-ingly, if this method is put into industrial practice, there will be a great disadvantage from the viewpoint of economy and, in particular, environmental protectlon.
In the reaction of an aromatic compound with chlorosulfonic acid, an aromatic sulfonic acid and a diaryl sulfone are formed as by-products, along with the desired aromatic sulfonyl chloride For example, when 1 mole of chlorobenzene is reacted with 3 moles of chlorosulfonic acid, 4,4'-dichloro-diphenyl sulfone is formed as a by-product in a 12~
. .
.
126P54~9~
yield, along with 4-chlorobenzenesulfonyl chloride (61% yield) [F. Ullmann et al., Ber., 40, 641(1907~].
It is also stated in the aforementioned article by A. M. Grigorovskiy et al. that, when chlorosulfonic acid is used at a molar ratio of 3, 4-chlorobenzene-sulfonic acid (20% yield) and 4,4'-dichlorodiphenyl sulfone (8% yield) are formed as by-products. It is generally said that chloroform and carbon tetra-chloride are useful for the purpose of suppressing side reactions in the reaction of an aromatic compound with chlorosulfonic acid [New Lectures on Experi~ental Chemistry, Vol. 14, "Syntheses and Reactions of Organic Compounds (III)", pp. 1787-1788, ~aruzen (1978)]. When chlorobenzene is reacted with chlorosulfonic aci.d in such a solvent (for exa.mple, when 1 mole of chlorobenzene is reacted with 3 moles of chlorosulfonic acid in chloroform), no by-product worthy of mention is formed, but the yield of 4-chlorobe~zenesulfonyl chloride is as low as 74.6%
20 (Japanese Patent Publication No. 19457/'67).
In order to enhance the yield of 4-chloro-benzenesulfonyI chloride, there is a well-known method in which chlorosul.fonic acid is reacted with sodium 4-chlorobenzenesulfonate. As described in the aforementioned article by Grigorovskiy et al., 1~5~
this method enables the desired product to be prepared in an 80% yield. It is also well known that this method can be carried out in an organic sol~en-t. Specifically, there has been proposed a process in which 4-chlorobenzenesulfonyl chloride is prepared in a yield of as high as 89% by suspending dried sodium 4-chlorobenzenesulfonate in chloroform and then reacting it with chlorosulfonic acid in an amount of 2 moles per mole of the sodium 4-chloro-benzenesulfonate [M. Kulka, J. Am. Chem. Soc., 72,1215(1950)~.
Although the amount of chlorosulfonic acid used is small and the yield is satisfactorily high, this process has the disadvantage that sodium 4-chlorobenzenesulfonate serving as one of the raw materials must be isolated and used in an anhydrous state. Thus, this process is not regarded as advantageous from an industrial point of view because it cannot be carried out economically.
Judging from these existing conditions of the art, it is a vital industrial problem concerning the reaction of chlorobenzene with chlorosulfonic acid to decrease the amount of chlorosulfonic acid used, suppress the formation of by-products, and obtain 4-chlorobenzenesulfonyl chloride in high yield.
- It is widely known that 4,4l-dichloro-diphenyl sulfone can be prepared by the Friedel-Crafts reaction in which 4-chlorobenzenesulfonyl chloride is reacted with chlorobenzene by using anhydrous ferric chloride as the catalyst [see, for e~ample, U.S. Patent 3,334,146(1967) and the like3.
In carrying out this process, however, it lS essen-tial to use 4-chlorobenzenesulfonyl chloride in an anhydrous s~ate.
As stated before, 4-chlorobenzenesulfonyl ehloride ean be prepared by reacting chlorobenzene with a stoiehiometrically exeessive amount of chlorosulfonic acid and then pouring the reaction mixture into ice water~ In this process, 4,4'-dichlorodiphenyl sulfone is formed as a by-product.
Accordingly, when the reaetion mixture containing 4-ehlorobenzenesulfonyl ehloride and 4,4'-dichloro-diphenyl sulfone is poured into ice water and the resulting mixture is heated to 90~C, 4-chloro-benzenesulfonyl chloride is hydrolyzed to 4-chlorobenzenesulfonic acld. Accordingly~ this process also serves to prepare 4,4'-dichlorodiphenyl sulfone by isolating the 4-chlorobenzenesulfonic acid so formed [U.S. Patent 2,860,168(1958)].
As is obvious from this fact, 4-ehloro-benzenesulfonyl ehloride is easily hydrolyzed to ~s~
4-chlorobenzenesulfonic acid. Accordingly, if it is desired to subject 4-chlorobenzenesulfonyl chloride - obtained as above to the Friedel-Crafts reaction with chlorobenzene, it must be dehydrated by, after completion of the reaction, pouring the reaction mixture into ice water, separating the product by filtration, and then drying it under reduced pressure.
However, in preparing 4-chlorobenzenesulfonyl chloride by the reaction of chlorobenzene with chlorosulfonic acid, a process including the steps of pouring the reaction mixture into ice water, separating the product by filtration, and drying to dehydra~e it cannot be regarded as an industrially satisfactory one from the viewpoint of manufacturing operation and economy.
In view of these facts, it is another vital industrial problem concerning the reaction of chloro-benæene with chlorosulfonic acid to decrease the amount of chlorosulfonic acid used, suppress the formation of by-products, and obtain anhydrous 4-chlorobenzenesulfonyl chloride in high yield.
Furthermore, a number of processes are conventionally known in which chlorobenzene used as a starting material is chlorosulfonylated and then converted into 4,4-dichlorodiphenyl sulfone without 5~
isolatlng the intermediate product. They include, for example, (1) a process in which chlorobenzene is reacted wi-th sulfur trioxide to form 4-chlorobenzenesulfonic acid, a chlorinating agent or thionyl chloride is allowed to act thereon, and the 4-chloro-benzenesulfonyl chloride so formed is condensed with chlorobenzene (Japan~se Pa-tent Publication ~o. $386/'81);
0 (2) a process in which chlorobenzene is reacted with both sulfur trioxide and thionyl chloride, and the 4-chlorobenzenesulfonyl chloride so formed is condensed with chlorobenzene [U.S.S.R.
568,637, Chem. Abstr., 87, 167728 b(l977)]; and 5 (3) a process in which chlorobenzene is reacted with chlorosu~lfonic acid to form 4-chlorobenzene-sulfonic acid, phosphorus oxychloride is reacted -therewith, and the 4-chlorobenzenesulfonyl chloride so formed is condensed with chloro-benzene [U.S. Patent 3,125,604(196~)].
In these processes, unexpensive sulfonating agents such as sulfur trioxide and chlorosulfonic acid are used. However, the chlorinating agents used therein, i.e. thionyl chloride and phosphorus 5 oxychloride, are relatively expensive and, therefore, the excess chlorinatiny agent is recovered after completion of the reaction. Accordingly, if these processes are put into industrial practice, there will be the disadvantages that provision for the recovery of the chlorinating agent must be made and the reuse of the recovered chlorinating agent is relatively difficult because it is easily decomposable. Thus, as a means for the industrial production of 4,4'-dichlorodlphenyl sulfone, none of the above-described processes are considered to be satisfactory from the viewpoint of both manufacturing operation and economy.
On the other hand, it is widely known that 4-chlorobenzenesulfonyl chloride is formed by reacting chlorobenzene with a stoichiometric amount of chlorosulfonic acid. However, if it i5 intended to form 4-chlorobenzenesulfonyl chloride according to this method and then subject it to the Friedel-Crafts reaction without isolating it, consideration must be given to the theoretical amount of sulfuric acid formed as a by-product. More specifically, it is necessary to prepare anhydrou~s 4-chlorobenzenesulfonyl chloride by, after completion of the reaction, pouring the reaction mixture into ice water and passing the resulting mixture through filtering, water-washing and drying steps, and then subjecting this inter-mediate product to condensation reaction with 5~
chlorobenzene. Thus, this method is not advantageous from an industrial point of view.
Nevertheless, the method using chloro-benzene and chlorosulfonic acid as the raw materials has the advantage that chlorosulfonic acid is easy to handle and industrially inexpensive. Accordingly, it is desirable in this ~ield of industry to prepare 4,4'-dichlorodiphenyl sulfone by reacting chlorobenzene with chlorosulfonic acid to form 4-chlorobenezene-sulfonyl chloride in an anhydrous state withoutisolating it, and then reacting it with chlorobenzene in the presence of ferric chloride.
Summary of the Invention It is an object of an aspect of the present invention to provide a process for the preparation of 4-chlorobenzenesulfonyl chloride with industrial advantages.
It is an object of an aspect of the present invention to provide a process for the preparation of anhydrous 4-chlorobenzenesulfonyl chloride with industrial advantages.
It is an object of an aspect of the present invention to provide a process for the preparation of 4,4'-dichlorodiphenyl sulfone from chlorobenzene and chlorosulfonic acid via anhydrous 4-chlorobenzene-sulfonyl chloride with industrial advantages.
S~a9~
lOa-Various aspects of the invention are as follows:
A process for the preparation of 4-chlorobenzene-sulfonyl chloride which comprises reacting chlorobenzene with chlorosulfonic acid in at least one organic solvent selected from the group consisting of halogenated aliphatic hydrocarbons in the presence of at least one compound selected from the group consisting of alkali metal salts of mineral acids and ammonium salts of mineral acids, thereby forming 4-chlorobenzenesulfonyl chloride, the chlorosulfonic acid being used in an amount of 2.5 to 4.0 moles per mole of the chlorobenzene.
A process for the preparation of 4,4'-dichlorodi-phenyl sulfone which comprises (a) reacting chlorobenzene with chlorosulfonic acid in a halogena-ted aliphatic hydrocarbon solvent in the presence of an alkali metal salt of a mineral acid and/or an ammonium salt of a mineral acid, the chlorosulfonic acid being used in an amount of 2.5 to 4.0 moles per mole of the chlorobenzene, 0 (b) washing the resulting reaction mix-ture with water, separating the organic solvent layer, and distilling off water, together with the organic solvent, to obtain 4-chlorobenzenesulfonyl chloride in an anhydrous state; and 5 (c) reacting the resulting anhydrous 4-chlorobenzene-sulfonyl chloride with chlorobenzene in the presence of a catalytic amount of ferric chloride.
~2~59~
According to the present invention, 4-chlorobenzenesulfonyl chloride can be prepared in high yield by reacting chlorobenzene with chloro-sulfonic acid in a halogenated aliphatic hydrocarbon solvent in the presence of an alkali metal salt of a mineral acid and/or an an~nonium salt of a mineral acid.
Moreover, anhydrous 4~chlorobenzenesulfonyl chlorid~ can be prepared hy reacting chlorobenzene with chlorosulfonic acid in a halogenated aliphatic hydrocarbon solvent in the presence of an alkali metal salt of a mineral acid and/or an ammonium salt of a mineral acid, washing the resulting reactio~n mixture with water, and then distilling off water, together with the sol.vent, from the separated organic solvent layer.
Furthermore, 4,4'-dichlorodiphenyl sulfone can be obtained by reacting anhydrous 4-chloro-benzenesulfonyl chloride obtained as above with chlorobenzene in the presence of a catalytic amount of ferric chloride.
Detailed Description of the Invention In the process of the present invention, the reaction of chlorobenzene with chlorosulfonic acid is carried out in a halogenated aliphatic ~5~
hydrocarbon solvent in the presence of an alkali metal salt of a mineral acid and/or an ammonium salt of a mineral acid.
The solvents which can be used in the process of the present invention are halogenated aliphatic hydrocarbons and, among others, halogenated lower aliphatic hydrocarbons of 1 or 2 carbon atoms having some or all of the hydrogen replaced with a halogen are preferred. Examples of such halogenated aliphatic hydrocarbons include dichloromethane, chloroform, c~rbon tetrachloride, 1,1 dichloroethane, 1,2-dichloroethane, l,l,l-trichloeroethane, 1,1,2-trichloroethane, 1,1,1,2-tetrachloroethane, 1,1,2,2-tetrachloroethane, 1,2-dichloroethylene, trichloro-ethylene, tetrachloroethylene, pentachloroethylene, hexachloroethylene, and analogous compounds obtained by replacing some or all of the chlorine with other halogensO Although no particular limitation is placed on the amount of solvent used, it is usually 20 used in an amount of 0.5 to 5.0 times, preferably 1.0 to 3.0 times, the weight of the chlorobenzene.
Useful alkali metal salts of mineral acids include the halogenides, sulfates, sulfites, nitrates and phosphates of lithium~ sodium and potassium.
Useful ammonium salts of mineral acids include .
ammonium chloride, ammonium bromide, amrnonium iodide, ammonium sulfate, ammonium sulfite, ammonium nitrate and ammonium phoshphate. If desired, these alkali metals sal-ts of mineral acids and ammonium salts of mineral acids may be used in combination. Such an alkali metal salt of a mineral acid and/or an ammonium salt of a mineral acid are used in an amount of 0.01 to 5 moles, preferably 0.05 to 2 moles, per mole of the chlorobenzene. Although the alkali metal salt and/or ammonium salt may be used in an amount of more than 5 moles per mole of the chlorobenzene, a molar ratio of 5 or less suffices to produce satis-factory effects.
In the process of the present invention, the effects of the solvent and the mineral acid salt(s) ar~ as follows: For example, when 1 mole of chlorobenzene is reacted with 3 moles of chloro-sulfonic acid at 55-60C, 4-chlorobenzenesulfonyl chloride is obtained in a 70% yield and 4,4'-dichlorodiphenyl sulfone is formed in a 9% yield~Moreover, when the aforesaid reaction is carried out using 1,2-dichloroethane as the solvent, the desired produc-t is obtained in a 69% yield and the corre-sponding sulfone is formed in a 10% yield. These results indicate that the solvent has no effect on .
~2~S~
the yield of the desired product and the formation of by-products. ~ext, when 1 mole of chlorobenzene is reac~ed with 3 moles of chlorosulfonic acid a-t the aforesaid temperature in the presence of 0.3 mole of sodium chloride, the desired product is obtained in a 75~ yield, but the sulfone formed as a by-product is decreased. Although the addition of sodium chloride enhances the yield of the desired product only slightly, it is a noteworthy fact that the formation of the sulfone by-product is suppressed.
On the other hand, when the same reaction is carried out accordin~ to -the present invention (that is, 1 mole of chlorobenzene is reacted with 3 moles of chlorosulfonic acid at 55-60C in 1,2-dichloroethane in the presence of 0.3 mole of sodium chloride), the yield of the desired product is markedly increased to 90% and the yield of the by-product is as low as 2.5~. In addition to sodium chloride, alkali metal salts (e.g., lithium, sodium and potassium salts) and ammonium salts of mineral acids (e.g., hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, sulfurous acid, nitric acid, phosphoric acid, etc.) can also produce similar effects.
~hus, by reacting chlorobenzene with chlorosulfonic acid in a halogenated aliphatic .
12t;1 5~
h~drocarbon solvent in the presence of an alkali metal salt of a mineral acid and/or an ammonium salt of a mineral acid, it is possible to prepare the desired product in high yield while suppressing the formation of by-products.
The amounts of chlorobenzene and chloro-sulronic acid used in the process of the present invention are usually such tha-t 2.5 to 4.0 moles, preferably 3.0 to 3.5 moles, of chlorosulfonic acid is provided for each mole of chlorobenzene. The reaction temperature generally ranges from 0 to 100C, the preferred ranye being from 10 to 90~.
No particular limitation is placed on the manner in which the process of the present invention lS is carried out, so long as chlorobenzene can be mixed and reacted ~ith chlorosulfonic acid. Usually, chlorobenzene is added dropwise to a mixture consist-ing of chlorosulfonic acid, an alkali metal salt of a mineral acid and/or an ammonium salt of a mineral acid, and an organic solvent. According to circum-stances, chlorosulfonic acid may be added dropwise to a mixture consisting of chlorobenzene, an alkali metal salt of a mineral acid and/or an ammonium salt of a mineral acid, and an organic solvent. After completion of the addition, the resulting reaction .
.
~f~05~
mixture is stirred at a predetermined temperature for a predetermined reaction time. Then, the reaction mixture is poured into ice water and the organic layer is separated. After the organic layer is washed with water and dried, the solvent is removed therefrom by distillation under reduced pressure to obtain the desired product, or 4-chloro-benzenesulfonyl chloride.
In a preferred embodiment of the present invention, anhydrous 4-chlorobenzenesulfonyl chloride can be obtained. Specifically, after completion of the reaction, the reaction mixture is usually cooled to room temperature and then washed with a sufficient amount of water to remove any by-product sulfuric acid and unreacted chlorosulfonic acid that are present in the reaction mixture. More specifically, the reaction mixture is usually washed by adding water thereto in an amount of, but not limited to t 5 to 6 times the weight of chlorosulfonic acid used.
Thereafter, the organic solvent layer is separated.
The solution so separated is heated under atmospheric pressure to distill off the water contained therein, together with the solvent, and thereby ob-tain 4-chlorobenzenesulfonyl chloride in an anhydrous state.
Although 4-chlorobenzenesulfonyl chloride .. . . I . , .. . ~ .
has the property of being easily hydxolyzed to 4-chlorobenzenesulfonic acid by heating it with water, the present invention enables 4-chloro-benzenesulfonyl chloride to be readily prepared in an anhydrous state.
To this end, the reaction mixture resulting from the reaction of chlorobenzene with chlorosulfonic acid in a halogenated aliphatic hydrocarbon solvent is washed with water to remove any by-product sulfuric acid and unreacted chlorosulfonic acid, and the separated organic solvent is then heated to distill off the water contained therein as the azeotropic mixture with the solvent, whereby 4-chlorobenzene-sul~onyl chloride can be obtained without being hydrolyzed to 4-chlorobenzenesulfonic acid. This is a quite unexpected and surprising fact in view of the prior art and the instability of 4-chlorobenzene~
sulfonyl chloride to water.
According to the present invention, anhydrous 4-chlorobenzenesulfonyl chloride can be prepared in the above-described manner. Therefore, it can be directly reacted with chlorobenzene in the presence of a catalytic amount of ferric chloride to produce 4,4'-dichlorodiphenyl sulfone industrially.
Specifically, chlorobenzene and ferric chloride are added to anhydrous 4-chlorobenzenesulfonyl chloride .5~
obtained as described above. The resulting reaction mixture is stirred at a predetermined temperature for a predetermined reaction time. After completion of the reaction, chlorobenzene is added to the reaction mixture so that its sulfone concentration may be adjusted to approximately 35 to 40%. After being cooled to a temperature of 65 to 70C, the reaction mixture is washed with water at that temperature to remove the ferric chloride. Subsequently, the chlorobenzene is removed by steam distillation to obtain crysta s of 4,4'-dichlorodiphenyl sulfone.
Since the process of the present invention permits 4-chlorobenzenesulfonyl chloride to be prepared in an anhydrous state and in high yield, it can be used directly, i.e. without being isolated, in the production of 4,4'-dichlorodiphenyl sulfone.
This indicates that the process of the present invention has a great industrial value.
In the above-described preparation of 4,4'-dichlorodiphenyl sulfone by reacting anhydrous 4-chlorobenzenesulfonyl chloride with chlorobenzene in the presence of anhydrous ferric chloride, the amount of chlorobenzene used is not critical so long as it is in the range of 1.5 to 2.5 moles per mole of the 4-chlorobenzenesulfonyl chloride. The ferric 5~
chloride is usually used in an amount of 2 to 5 mole % based on the 4-chlorobenzenesulfonyl chloride, and greater amounts produce no additional effect.
The reaction tempera~ure ranges from 140 to 160C.
The progress of the reaction can be readily followed by gas chromatography or high-speed liquid chromato-graphy. Generally, the reaction is completed in 10 to 20 hours.
Thus, according to the present invention, 4,4'-dichlorodiphenyl sulfone can be prepared from chlorobenzene and chlorosulfonic acid with industrial advantages. ~lore specifically, 4,4'-dichlorodiphenyl sulfone can be prepared in high yield by reacting chlorobenzene with chlorosulfonic acid and then reacting the intermediate product with chlorobenzene without isolating it.
The present invention is further illustrated by the following ~xamples.
Example 1 In 250 g of 1,2-dichloroethane were suspended 349 g (3.0 moles) of chlorosulfonic acid and 17.5 g (0.3 mole) of sodium chloride. While this suspension was kept at a temperature of 55-60C, 112.5 g (1.0 mole) of chlorobenzene was added drop-wise thereto over a period of 3 hours. The resulting . .
~. .
reaction mixture was stirred at that temperature for an additional 5 hours, cooled to room temperature, and then poured into 1 liter of ice wa-ter. After this mixture was stirred well, the organic layer was separated therefrom. The same procedure was repeated by using 1 liter of ice water. After drying the separated organic layer, the solvent was removed -therefrom by distillation under reduced pressure to obtain crystals of 4-chlorobenzenesulfonyl chloride.
The results are shown in Table 1.
Examples 2 to 13 The desired product was obtained by repeat-ing the procedure of Example 1, except that the amount of chlorosulfonic acid used, the type and amount of alkali metal salt or ammonium salt used, the type and amount of solvent used, and the reaction temperature were varied as indicated in Table 1. The results are shown in Table 1.
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Example 1~
In 250 g of 1,2-dichloroethane were suspended 349 g (3.0 moles) of chlorosulfonic acid and 17.5 g (0.3 mole) of sodium chloride. While this suspension was kept at a temperature of 55-60C, 112.5 g (1.0 mole) of chloroben~ene was added dropwise thereto over a period of 3 hours. The resulting reaction mixture was stirred a-t that temperature for an additional 5 hours and then cooled to room temperature. After the reaction mixture was washed by the ~ddition of 1 liter of water/ the organic layer was separated therefrom. The same procedure was repeated by using 1 liter of water.
The separated solution was heated to distill off the lS solvent and thereby obtain crystals of ~-chloro-benzenesulfonyl chloride. The results are shown in Table 2.
E~amples 15 to 26 The desired product was obtained by repeating the procedure of Example 1~, except that the amount of chlorosulfonic acid used, the type and amount of alkali metal salt or ammonium salt used, the type and amount of solvent used, and the reaction temperature were varied as indicated in Table 2. The results are shown in Table 2.
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Example 1~
In 250 g of 1,2-dichloroethane were suspended 349 g (3.0 moles) of chlorosulfonic acid and 17.5 g (0.3 mole) of sodium chloride. While this suspension was kept at a temperature of 55-60C, 112.5 g (1.0 mole) of chloroben~ene was added dropwise thereto over a period of 3 hours. The resulting reaction mixture was stirred a-t that temperature for an additional 5 hours and then cooled to room temperature. After the reaction mixture was washed by the ~ddition of 1 liter of water/ the organic layer was separated therefrom. The same procedure was repeated by using 1 liter of water.
The separated solution was heated to distill off the lS solvent and thereby obtain crystals of ~-chloro-benzenesulfonyl chloride. The results are shown in Table 2.
E~amples 15 to 26 The desired product was obtained by repeating the procedure of Example 1~, except that the amount of chlorosulfonic acid used, the type and amount of alkali metal salt or ammonium salt used, the type and amount of solvent used, and the reaction temperature were varied as indicated in Table 2. The results are shown in Table 2.
.
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~ - ---- - - -- - - - -Example 27 In 250 g of 1,2-dichloroethane were suspended 349 g (3.0 moles) of chlorosulfonic acid and 17.5 g (0.3 mole) of sodium chloride. While this suspension was kept at a temperature of 55-60C, 112.5 g (1.0 mole) of chlorobenzene was added drop-wise thereto over a period of 3 hours. The resulting reaction mixture was stirred at that temperature for an additional 5 hours and then cooled to room temper-ature. After the reaction mixture was washed by theaddition of 1 liter of water, the organic layer was separated therefrom. The same procedure was repeated by using 1 liter of water. The separated solution was heated to distill off the solvent and thereby obtain crystals of 4-chlorobenzenesulfonyl chloride.
I'o this product were added 214 g (1.9 moles) of chlorobenzene and 3.1 g of ferric chloride. While being kept at 145-155C, this reaction mixture was stirred for 15 hours. After the addition of 250 g of chlorobenzene, the resulting mixture was cooled to 70~ and washed at that temperature by the addition of 1 liter o water. After the organic layer was separated, chlorobenzen~ was removed therefrom by steam distillation to obtain crystals of 4,4l_ dichlorodiphenyl sulfone. The results are shown in Table 3.
~2~5~
Examples 28 to 39 The desired product was obtained by repeat-ing the procedure of Example 27, except that the amount of chlorosulfonic acid used, the type and amount of alkali metal salt or ammonium salt used, the type and amount of solvent used, and the reaction temperature were varied as indicated in Table 3.
The results are shown in Table 3.
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~ - ---- - - -- - - - -Example 27 In 250 g of 1,2-dichloroethane were suspended 349 g (3.0 moles) of chlorosulfonic acid and 17.5 g (0.3 mole) of sodium chloride. While this suspension was kept at a temperature of 55-60C, 112.5 g (1.0 mole) of chlorobenzene was added drop-wise thereto over a period of 3 hours. The resulting reaction mixture was stirred at that temperature for an additional 5 hours and then cooled to room temper-ature. After the reaction mixture was washed by theaddition of 1 liter of water, the organic layer was separated therefrom. The same procedure was repeated by using 1 liter of water. The separated solution was heated to distill off the solvent and thereby obtain crystals of 4-chlorobenzenesulfonyl chloride.
I'o this product were added 214 g (1.9 moles) of chlorobenzene and 3.1 g of ferric chloride. While being kept at 145-155C, this reaction mixture was stirred for 15 hours. After the addition of 250 g of chlorobenzene, the resulting mixture was cooled to 70~ and washed at that temperature by the addition of 1 liter o water. After the organic layer was separated, chlorobenzen~ was removed therefrom by steam distillation to obtain crystals of 4,4l_ dichlorodiphenyl sulfone. The results are shown in Table 3.
~2~5~
Examples 28 to 39 The desired product was obtained by repeat-ing the procedure of Example 27, except that the amount of chlorosulfonic acid used, the type and amount of alkali metal salt or ammonium salt used, the type and amount of solvent used, and the reaction temperature were varied as indicated in Table 3.
The results are shown in Table 3.
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Claims (15)
1. A process for the preparation of 4-chlorobenzene-sulfonyl chloride which comprises reacting chlorobenzene with chlorosulfonic acid in at least one organic solvent selected from the group consisting of halogenated aliphatic hydrocarbons in the presence of at least one compound selected from the group consisting of alkali metal salts of mineral acids and ammonium salts of mineral acids, thereby forming 4-chlorobenzenesulfonyl chloride, the chlorosulfonic acid being used in an amount of 2.5 to 4.0 moles per mole of the chlorobenzene.
2. The process according to claim 1 wherein the reaction is carried out at a temperature of 0° to 100°C.
3. The process according to claim 1 wherein the halogenated aliphatic hydrocarbons have one or two carbon atoms.
4. The process according to claim 1 wherein the organic solvent is used in an amount of 0.5 to 5.0 times the weight of the chlorobenzene.
5. The process according to claim 1 wherein the compound is selected from the group consisting of (a) a halogenide, sulfate, sulfite, nitrate or phosphate of lithium, (b) a halogenide, sulfate, sulfite, nitrate or phosphate of sodium, (c) a halogenide, sulfate, sulfite, nitrate or phosphate of potassium, and (d) ammonium chloride, ammonium bromide, ammonium iodide, ammonium sulfate, ammonium sulfite, ammonium nitrate or ammonium phosphate.
6. The process according to claim 1 wherein the compound is used in an amount of 0.01 to 5 moles per mole of the chlorobenzene.
7. The process according to claim 1 wherein the chlorosulfonic acid is used in an amount of 3.0 to 3.5 moles per mole of the chlorobenzene.
8. The process according to claim 2 wherein the reaction is carried out at a temperature of 10° to 90°C.
9. The process according to claim 4 wherein the organic solvent is used in an amount of 1.0 to 3.0 times the weight of the chlorobenzene.
10. The process according to claim 1 wherein the reaction is carried out by adding the chlorobenzene dropwise to a mixture of the chlorosulfonic acid, the compound and the organic solvent.
11. The process according to claim 1 which further comprises washing the resulting reaction mixture with water and then distilling off water, together with the organic solvent, from the organic solvent layer to obtain 4-chlorobenzenesulfonyl chloride in an anhydrous state.
12. The process according to claim 11 wherein the amount of water used in washing the reaction mixture is sufficient to remove any by-product sulfuric acid unreacted chlorosulfonic acid that are present in the reaction mixture.
13. The process according to claim 11 wherein the washing is carried out by adding water to the reaction mixture in an amount of 5 to 6 times the weight of chloro-sulfonic acid used and then stirring the resulting mixture.
14. The process according to claim 11 wherein the washing is carried out at room temperature.
15. A process for the preparation of 4,4'-dichlorodi-phenyl sulfone which comprises (a) reacting chlorobenzene with chlorosulfonic acid in a halogenated aliphatic hydrocarbon solvent in the presence of an alkali metal salt of a mineral acid and/or an ammonium salt of a mineral acid, the chloro-sulfonic acid being used in an amount of 2.5 to 4.0 moles per mole of the chlorobenzene;
(b) washing the resulting reaction mixture with water, separating the organic solvent layer, and distilling off water, together with the organic solvent, to obtain 4-chlorobenzenesulfonyl chloride in an anhydrous state; and (c) reacting the resulting anhydrous 4-chlorobenzene-sulfonyl chloride with chlorobenzene in the presence of a catalytic amount of ferric chloride.
(b) washing the resulting reaction mixture with water, separating the organic solvent layer, and distilling off water, together with the organic solvent, to obtain 4-chlorobenzenesulfonyl chloride in an anhydrous state; and (c) reacting the resulting anhydrous 4-chlorobenzene-sulfonyl chloride with chlorobenzene in the presence of a catalytic amount of ferric chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000422389A CA1205491A (en) | 1983-02-25 | 1983-02-25 | Process for the preparation of 4- chlorobenzenesulfonyl chloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000422389A CA1205491A (en) | 1983-02-25 | 1983-02-25 | Process for the preparation of 4- chlorobenzenesulfonyl chloride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1205491A true CA1205491A (en) | 1986-06-03 |
Family
ID=4124645
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000422389A Expired CA1205491A (en) | 1983-02-25 | 1983-02-25 | Process for the preparation of 4- chlorobenzenesulfonyl chloride |
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| Country | Link |
|---|---|
| CA (1) | CA1205491A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5136043A (en) * | 1989-06-17 | 1992-08-04 | Hoechst Aktiengesellschaft | Process for the preparation of aromatic sulfonyl chlorides |
-
1983
- 1983-02-25 CA CA000422389A patent/CA1205491A/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5136043A (en) * | 1989-06-17 | 1992-08-04 | Hoechst Aktiengesellschaft | Process for the preparation of aromatic sulfonyl chlorides |
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