GB2087386A - Process for producing chlorobenzene sulfochloride - Google Patents
Process for producing chlorobenzene sulfochloride Download PDFInfo
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- GB2087386A GB2087386A GB8130118A GB8130118A GB2087386A GB 2087386 A GB2087386 A GB 2087386A GB 8130118 A GB8130118 A GB 8130118A GB 8130118 A GB8130118 A GB 8130118A GB 2087386 A GB2087386 A GB 2087386A
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- Prior art keywords
- chlorobenzene
- sulfochloride
- sulfuric acid
- layer
- water
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- JESCPVSKEGXYSC-UHFFFAOYSA-N chlorobenzene;sulfurochloridic acid Chemical compound OS(Cl)(=O)=O.ClC1=CC=CC=C1 JESCPVSKEGXYSC-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 238000000034 method Methods 0.000 title claims abstract description 31
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 216
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims abstract description 112
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims abstract description 72
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 66
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002244 precipitate Substances 0.000 claims abstract description 16
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 239000011541 reaction mixture Substances 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims description 21
- 239000002351 wastewater Substances 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 abstract description 7
- 239000007795 chemical reaction product Substances 0.000 description 32
- 239000007791 liquid phase Substances 0.000 description 12
- MNURPFVONZPVLA-UHFFFAOYSA-N 2-chlorobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1Cl MNURPFVONZPVLA-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000005191 phase separation Methods 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- CKAPSXZOOQJIBF-UHFFFAOYSA-N hexachlorobenzene Chemical compound ClC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl CKAPSXZOOQJIBF-UHFFFAOYSA-N 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- -1 if necessary Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
- C07C303/08—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with halogenosulfonic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A process for producing chlorobenzene sulfochloride comprises adding a reaction mixture of chlorobenzene and chlorosulfonic acid to water or diluted sulfuric acid to decompose excess chlorosulfonic acid; driving off hydrogen chloride thereby generated, from the system; bringing the sulfuric acid concentration in the sulfuric acid layer upon completion of the decomposition to be from 60 to 90%; and then separating chlorobenzene sulfochloride. The chlorobenzene sulfochloride is separated in a liquid state at a temperature of from 50 to 80 DEG C. Further, water used to wash and purify the chlorobenzene sulfochloride is reused as a water source for the decomposition of the excess chlorosulfonic acid in the process. Furthermore, the sulfuric acid layer separated from the chlorobenzene sulfochloride layer is cooled to separate a precipitate, which is then reused as a feed material for the preparation of the reaction mixture of chlorobenzene and chlorosulfonic acid.
Description
SPECIFICATION
Process for producing chlorobenzene sulfochloride
The present invention relates to a process for producing chlorobenzene sulfochloride which comprises adding a reaction product (reaction mixture herein) of chlorobenzene and chlorosulfonic acid to water or diluted sulfuric acid thereby to decompose excess chlorosulfonic acid.
Particularly, the present invention relates to a process for producing chlorobenzene sulfochloride, which comprises:
1) adding a reaction product of chlorobenzene and chlorosulfonic acid to water or diluted sulfuric acid to decompose excess chlorosulfonic acid, driving off hydrogen chloride thereby generated, from the system, bringing the sulfuric acid concentration in the sulfuric acid layer upon completion of the decomposition to be from 60 to 90%, separating chlorobenzene sulfochloride from the sulfuric acid layer in a liquid state at a temperature of not less than 50 C, 2) adding an inert organic solvent to the obtained chlorobenzene sulfochloride layer to prepare a solution, then washing with a small amount of water, reusing the waste water after the washing as the water component for decomposing the excess chlorosulfonic acid in the reaction product of chlorobenzene and chlorosulfonic acid, or as a diluting water component for adjusting the diluted sulfuric acid to be used for the sampe purpose,
3) cooling the sulfuric acid layer obtained as mentioned above, to separate a precipitate, and reusing the precipitate as a feed material for the preparation of the reaction product of chlorobenzene and chlorosulfonic acid.
Chlorobenzene sulfochloride is commonly used as an intermediate for the production of monomers for polymer compounds, or as an intermediate for the production of pharmaceuticals or agricultural medicines.
In the production of chlorobenzene sulfocholride by the reaction of chlorobenzene and chlorosulfonic acid, the reaction formula is represented as follows:
According to this reaction, hydrogen chloride gas and sulfuric acid are produced as by-products at the same time as the formation of the desired chlorobenzene sulfochloride. Further, the second stage reaction is an equilibrium reaction, and it is usual that an excess amount of chlorosulfonic acid is used to increase the yield of chlorobenzene sulfochloride. Thus, the reaction product usually contains, in addition to the above mentioned sulfochloride and sulfuric acid, unreacted chlorosulfonic acid and a small amount of chlorobenzene sulfonic acid.In order to separate the sulfochloride from such a reaction product, it is common to employ a method which comprises dumping the above mentioned reaction product into a great amount of cold water or ice water thereby to decompose the unreacted chlorosulfonic acid into hydrogen chloride and sulfuric acid, and separating the sulfochloride precipitated in the cold water in a solid form.
However, in the separation of the sulfochloride according to the above method, a great amount of water is used, and accordingly, hydrochloric acid and sulfuric acid formed by the hydrolysis of chlorosulfonic acid are thereby diluted, and thus it becomes difficult to reuse them as recovered hydrochloric acid and recovered sulfuric acid. Accordingly, a great amount of waste water is thereby formed, and the method has a great economical disadvantage. Further, in the separation of the sulfochloride according to the above mentioned method, the temperature of the system is rapidly raised by the generation of heat due to the hydrolysis reaction of the unreacted chlorosulfonic acid and by the heat of dilution of sulfuric acid contained in the reaction product as well as sulfuric acid produced by the hydrolysis of the chlorosulfonic acid.
Accordingly, the method is considered to have a further disadvantage that the yield of the sulfochloride decreases as the desired sulfochloride undergoes a decomposition reaction due to the above mentioned heat.
Thus, when the above mentioned method is employed, it is common that the operation is carried out at a low temperature at a level of not more than about 30'C in order to suppress the decomposition reaction of the sulfochloride, and a great amount of energy is required for the cooling.
Further, as an improved method for the production, there has been proposed a method which comprises adding a reaction product of an aromatic hydrocarbon and chlorosulfonic acid to diluted acid thereby to decompose the excess amount of chlorosulfonic acid at a temperature of not more than 35"C, driving off hydrogen chloride thereby generated, from the system, bringing the sulfuric acid concentration in the sulfuric acid layer to be at least 70% and finally separating the aromatic sulfochloride from the sulfuric acid (Japanese Laid-Open Patent Application No.
100035/75), or a method in which hydrochloric acid of at least 20% is used instead of diluted sulfuric acid to suppress the heat of dilution of sulfuric acid, the excess amount of chlorosulfonic acid is decomposed at a temperature of not more than 35"C and under a condition that the sulfuric acid concentration in the sulfuric acid layer finally becomes to be not less than 70%, thereby to release hydrogen chloride, and the cooling is effectively carried out taking an advantage of the endothermic reaction of the releasing reaction (Japanese Laid-Open Patent
Application No. 55548/79).
However, the desired chlorobenzene sulfochloride has a melting point of about 53"C, and if the above mentioned methods are used, the chlorobenzene sulfochloride forms a thick slurry solid at a temperature of not more than 35"C, and at a sulfuric acid concentration as high as at least 70%, it is very difficult to separate it by filtration, and yet the separated solid component would contain substantial amounts of sulfuric acid and unreacted chlorobenzene sulfonic acid, and thus it is required to use a great amount of cold water for the purification of the sulfochloride. With these drawbacks, the above methods are industrially extremely disadvantageous and unacceptable.
Having these points in mind, the present inventors have investigated the relation between the decomposition rate of chlorobenzene sulfochloride and the temperature by contacting the chlorobenzene sulfochloride which has a melting point of about 53"C and which is solid at room temperature, with various concentrations of sulfuric acd. As a result, they have found a new fact that if the sulfuric acid concentration is from 60 to 90%, chlorobenzene sulfochloride does not substantially undergo decomposition even at a temperature higher than the temperature at which chlorobenzene sulfochloride forms a liquid phase, i.e. at a temperature higher than 50"C, and this is a discovery which breaks through the conventional general common knowledge.
Thus, the present invention has been accomplished.
Namely, according to the present invention, a reaction product of chlorobenzene and chlorosulfonic acid is dropwise added to water or diluted sulfuric acid in an amount measured to bring the sulfuric acid concentration in the sulfuric acid layer after completion of the above mentioned decomposition to a level of from 60 to 90%, thereby to decompose excess chlorosulfonic acid.
There is no particular restriction to the temperature at the time of the decomposition of the chlorosulfonic acid. However, in order to efficiently effect the decomposition, a proper temperature may be selected within a range from room temperature to 85"C. It is preferred that the temperature is selected within a range of from 40 to 75"C at which a small amount of a precipitate forms or the system is completely in a liquid state during the decomposition. Within this temperature range, the sulfochloride undergoes substantially no decomposition. As an example, Table 1 shows decomposition rates obtained by contacting chlorobenzene sulfochloride with sulfuric acid of various concentrations.Namely, 5 parts of chlorobenzene sulfochloride, the purity of which was preliminarily determined, was added in 50 parts of sulfuric acid having various concentrations as shown in Table 1 and stirred at 65"C for 2 hours, and thereafter the decomposition rate of the chlorobenzene sulfochloride was measured.
Table 1
Concentration of sulfuric 50 60 65 75 85 97 acid (% by weight)
Decomposition rate (%) 3.9 2.1 0.8 1.2 2.4 20
From the above results, it can be said that if the concentration of the sulfuric acid to be contacted, is from 60 to 90%, the chlorobenzene sulfochloride undergoes substantially no decomposition even at 65"C.
Thus, it is possible to carry out the decomposition of the excess chlorosulfonic acid in the reaction product of chlorobenzene and chlorosulfonic acid, at such a high temperature.
Accordingiy, the cooling operation from outside can thereby be simplified, and the time for the decomposition can be shortened. After completion of the decomposition of excess chlorosulfonic acid, if necessary, air or nitrogen may be blown in to drive off hydrogen chloride from the system. Then, the sulfuric acid layer and the chlorobenzene sulfochloride layer can readily be separated in a liquid state at 50 to 80"C, preferably at 60 to 75"C, without substantial decomposition of chlorobenzene sulfochloride.
The chlorobenzene sulfochloride layer thus separated has an adequately high purity as chlorobenzene sulfochloride by itself, i.e. without being further purified, and the amouts of the remaining sulfuric acid and chlorobenzene sulfonic acid are minimal.
However, when it is used for fine synthetic reactions, it is required to further improve the purity.
Therefore, the present inventors have conducted a further research for a purification method which is free from a loss of the chlorobenzene sulfochloride separated from the sulfuric acid layer and which does not bring about a waste. As a result, it has been found that the purification can readily be done simply by dissolving the chlorobenzene sulfochloride layer separated from the sulfuric acid layer in an inert organic solvent and thereafter washing it with a small amount of water, and, besides, all of the waste water after the washing, can be used as the water component for decomposing the excess chlorosulfonic acid in the reaction product of chlorobenzene and chlorosulfonic acid, or as the water component for preparing the diluted sulfuric acid to be used for the same purpose, and it is thereby possible to produce chlorobenzene sulfochloride in the same efficiency as in the case where pure water is used.
Namely, the present invention provides a process for producing superiorly purified chlorobenzene sulfochloride, and it provides a process in which no waste water is formed in the production of the purified chlorobenzene sulfochloride.
The inert organic solvent to be used in the present invention is a solvent in which chlorobenzene sulfochloride is adequately soluble without being decomposed, and which is insoluble or hardly soluble in water. For example, an aliphatic saturated hydrocarbon, an aromatic hydrocarbon, a halogenated aliphatic hydrocarbon and a halogenated aromatic hydrocarbon are used. Specific examples are hexane, heptane, octane, benzene, toluene, xylene, methylene chloride, chloroform, dichloroethane, trichloroethane, chlorobenzene and dichlorobenzene.
Further, the small amount of water to be used for washing the solution prepared by adding the inert organic solvent to the chlorobenzene sulfochloride layer, is meant for water in an amount of from 10 to 100 9 per 100 g of the chlorobenzene sulfochloride layer and which is less than the amount of water required to decompose the excess chlorosulfonic acid in the reaction product of chlorobenzene and chlorosulfonic acid and to eventually bring the sulfuric acid concentration in the sulfuric acid layer to a level of from 60 to 90%. lf the amount of water is within the above range, no waste water will be formed at the time of obtaining the purified chlorobenzene sulfochloride.
Namely, the waste water after the washing operation can all be reused as the water component for the de-composition of the excess chlorosulfonic acid in the reaction product of chlorobenzene and chlorosulfonic acid, or as the water component for the preparation of the diluted sulfuric acid to be used for the same purpose. Accordingly, in this purification step, no waste water will be formed.
Further, after separating the chlorobenzene sulfochloride layer in a liquid state, the obtained sulfuric acid layer is cooled and the precipitate is separated. The separated precipitate can be reused as it is or after subjecting it to azeotropic dehydration with chlorobenzene, as a feed material for the preparation of the reaction product of chlorobenzene and chlorosulfonic acid. It has been found that the yield of chlorobenzene sulfochloride per chlorobenzene used, can thereby be increased. Further, the purity of sulfuric acid is thereby improved, and thus the value of the regenerated sulfuric acid is increased for reutilization.
As mentioned above, according to the process of the present invention, the following useful results are obtainable.
(1) Chlorobenzene sulfochloride does not substantially undergo decomposition even when contacted with from 60 to 90% of sulfuric acid at a temperature higher than the temperature at which the sulfochloride turns into a liquid phase. Therefore, the sulfuric acid layer and the chlorobenzene sulfochloride layer can readily be separated in a liquid state.
(2) When the excess chlorosulfonic acid in the reaction product of chlorobenzene and chlorosulfonic acid is hydrolyzed, the temperature for the hydrolysis can be brought higher than room temperature, preferably to a high level of from 40 to 75"C. The cooling operation from outside such as temperature control can be simplified, and the time required for the hydrolysis can be shortened, thus bringing about an economical advantage.
(3) The chlorobenzene sulfochloride separated in a liquid state, contains minimal amounts of sulfuric acid and chlorobenzene sulfonic acid. Therefore, the purification operation to obtain a highly pure product can readily be made, and brings about little waste which requires aftertreatment. Thus, the economical merits thereby obtainable are substantial.
(4) As the sulfuric acid generated as a by-product can be recovered at a high concentration of from 60%-90%, it is possible to reuse the sulfuric acid for other usages.
(5) The hydrogen chloride generated as a by-product, does not accompany any substance having a low vapour pressure such as an organic solvent, and accordingly it can be recovered as highly pure hydrochloric acid and can therefore be reused.
(6) The waste water after the washing operation can all be reused as the water component for the decomposition of the excess chlorosulfonic acid in the reaction product of chlorobenzene and chlorosulfonic acid, or as the water component for the preparation of the diluted sulfuric acid to be used for the same purpose. Thus, this purification step yields no waste water.
(7) The major proportion of the precipitate obtained by cooling the sulfuric acid layer is unreacted chlorobenzene sulfonic acid, which can be used as the feed material for the preparation of the reaction product of chlorobenzene and chlorosulfonic acid. Thus, it is possible to increase the yield of chlorobenzene sulfochloride per chlorobenzene used.
(8) The major proportion of unreacted chlorobenzene sulfonic acid is removed from the sulfuric acid layer, and accordingly, the purity of the sulfuric acid is thereby improved and the value of the regenerated sulfuric acid is increased for reutilization. The regenerated sulfuric acid can be reused as a feed material for the preparation of the diluted sulfuric acid which is used for the decomposition of the excess chlorosulfonic acid.
Now, the invention will be described in further detail with reference to Examples, Comparative
Examples and Referential Examples. However, it should be understood that the present invention is not limited to these Examples.
Example 1
Fed into a flask was 524 9 (4.5 moles) of chlorosulfonic acid, and then 1 69 g (1.5 moles) of chlorobenzene was dropwise added thereto while cooling the system to maintain it at a temperature of not more than 60"C. It took about 30 minutes to complete the dropwise addition, and then the system was kept at 60"C for 2 hours. Then, the reaction product thereby obtained was dropwise added to 1 40 9 of water at a temperature of from 40 to 60"C for 20 minutes. After the completion of the dropwise addition, the reaction was aged at a temperature of from 60 to 65"C for 20 minutes, and then dried air was continuously blown into the reaction product to drive off the remaining hydrogen chloride from the system.Thereafter, the reaction product was transferred to a dropping funnel which was kept warm, and the liquid phase separation was carried out at a temperature of 65"C. The lower layer was a sulfuric acid layer, from which 424 g of sulfuric acid having a concentration of 73% was recovered. The upper layer was a chlorobenzene sulfochloride layer, from which 289 g of chlorobenzene sulfochloride having a purity of 90% was obtained. The yield based on the fed chlorobenzene was 82%.
Example 2
The operation was carried out in the same manner as in Example 1 except that the reaction product of chlorosulfonic acid and chlorobenzene was dropwise added to 788 9 of 60% sulfuric acid. After the liquid phase separation, about 1100 9 of sulfuric acid having a concentration of 73% was obtained from the lower layer. From the upper layer, 286 9 of chlorobenzene sulfochloride having a purity of 92% was obtained. The yield based on the fed chlorobenzene was 83%.
Example 3
The operation was carried out in the same manner as in Example 1 except that the reaction product of the chlorosulfonic acid and chlorobenzene was dropwise added to 284 9 of 60% sulfuric acid.
After the liquid phase separation, about 600 9 of sulfuric acid having a concentration of 85% was recovered from the lower layer. From the upper layer, 279 9 of chlorobenzene sulfochloride having a purity of 92% was obtained from the upper layer. The yield based on the fed chlorobenzene was 81%.
Example 4
The operation was carried out in the same manner as in Example 1 except that the reaction product was dropwise added to 683 9 of 40% sulfuric acid.
After the liquid phase separation, about 1000 g of sulfuric acid having a concentration of 60% was recovered from the lower layer. From the upper layer, 286 g of chlorobenzene sulfochloride having a purity of 92% was obtained. The yield based on the fed chlorobenzene was 83%.
Example 5
The operation was carried out in the same manner as in Example 2 except that the temperature for the liquid phase separation of the sulfuric acid layer and the chlorobenzene sulfochloride layer was 75"C.
After the liquid phase separation, about 1100 g of sulfuric acid having a concentration of 73% was recovered from the lower layer. From the upper layer, 282 9 of chlorobenzene sulfochloride having a purity of 91% was obtained. The yield based on the fed chlorobenzene was 81%.
Example 6
The operation was carried out in the same manner as in Example 2 except that the temperature for the liquid phase separation of the sulfuric acid layer and the chlorobenzene sulfochloride layer was 50"C.
After the liquid phase separation, about 1100 g of sulfuric acid having a concentration of 73% was recovered from the lower layer. From the upper layer, 289 g of chlorobenzene sulfochloride having a purity of 91% was obtained. The yield based on the fed chlorobenzene was 83%.
Comparative Example 1
The operation was carried out in the same manner as in Example 1 except that the reaction product of chlorosulfonic acid and chlorobenzene was dropwise added to 1 28 9 of 60% sulfuric acid.
After the liquid phase separation, about 450 9 of sulfuric acid having a concentration of 95% was recovered from the lower layer. From the upper layer, 253 9 of chlorobenzene sulfochloride having a purity of 85% was obtained. The yield based on the fed chlorobenzene was 68%. It is seen that the yield as well as the purity is considerably inferior to the Examples of the present invention.
Comparative Example 2
The operation was carried out in the same manner as in Example 1 except that the reaction product of chlorosulfonic acid and chlorobenzene was dropwise added to 1 628 g of 40% sulfuric acid.
After the liquid phase separation, about 1 960 g of sulfuric acid having a concentration of 50% was recovered from the lower layer. From the upper layer, 267 g of chlorobenzene sulfochloride having a purity of 90% was obtained The yield based on the fed chlorobenzene was 76%, which is considerably inferior to the Examples of the present invention.
Comparative Example 3
A reaction product of chlorosulfonic acid and chlorobenzene, was prepared in the same manner as in Example 1. Then, the reaction was dropwise added to 788 g of 60% sulfuric acid while maintaining the temperature of the system at a level of at most 25"C. Immediately after the commencement of the dropwise addition, the system turned into a slurry state, and finally became a thick slurry, whereby the stirring and the cooling were very difficult. Accordingly, it required 2 hours for the dropwise addition of the whole amount. After the completion of the dropwise addition, dry air was continuously blown into the product to drive off the remaining hydrogen chloride from the system.
Thereafter, the reaction product was filtered at 25"C, and sulfuric acid was sufficiently squeezed out, whereupon about 1030 g of sulfuric acid having a concentration of 73% was recovered.
The filtered product was chlorobenzene sulfochloride having a purity of 72%, and the amount thereof was 360 g. The yield based on the fed chlorobenzene was 82%. It is seen that the purity is considerably lower than the Examples of the present invention.
The following Referential Examples 1 and 2, and Examples 7 to 9 are concerned with the reuse of the water after the washing with water.
Referential Example 1
Added to the chlorobenzene sulfochloride layer separated from the sulfuric acid layer in Example 1, was 210 ml of chlorobenzene to prepare a solution. To the solution, 120 g of pure water was added at room temperature, and then the solution was stirred for 20 minutes and thereafter left to stand still for 30 minutes. Then, the water layer was separated. The amount of water layer thereby obtained was 1 35 g. From the chlorobenzene layer separated from the water layer, chlorobenzene was distilled off under reduced pressure, whereupon 274 g of chlorobenzene sulfochloride having a purity of 95% was obtained.
Referential Example 2
The operation was carried out in the same manner as in Referential Example 1 except that the reaction product of chlorosulfonic acid and chlorobenzene, was dropwise added to 788 g of 60% sulfuric acid prepared from 488 g of 97% sulfuric acid as a reagent and 300 g of pure water. By separating the sulfuric acid layer and the chlorobenzene sulfochloride layer, about 1100 g of sulfuric acid having a concentration of 73% was recovered from the lower layer.
From the upper layer, 286 g of chlorobenzene sulfochloride having a purity of 92% was obtained. The yield based on the fed chlorobenzene was 83%. After the washing with water, 1 29 g of a water layer and 277 g of chlorobenzene sulfochloride having a purity of 95% were obtained.
Example 7
The operation was carried out in the same manner as in Referential Example 1 except that the reaction product of chlorosulfonic acid and chlorobenzene, was dropwise added to 1 55 g of the water component prepared by mixing 1 35 g of the total amount of the water layer obtained after the washing with water in Referential Example 1 and 20 g of pure water. By separating the sulfuric acid layer and the chlorobenzene sulfochloride layer, about 450 g of sulfuric acid having a concentration of 73% was recovered from the lower layer. From the upper layer, 304 9 of chlorobenzene sufochloride having a purity of 85% was obtained. The yield based on the fed chlorobenzene was 82%. After the washing with water, 1 50 g of the water layer and 274 g of chlorobenzene sulfochloride having a purity of 95% were obtained.From the comparison with
Referential Example 1, it is seen that there is no difference in the purity or the yield of the purified chlorobenzene sulfochloride, even when the water component obtained after the washing with water in Referential Example 1 was used instead of the pure water.
Example 8
The operation was carried out in the same manner as in Referential Example 1 except that the reaction product was dropwise added to 803 9 of 60% sulfuric acid prepared from 488 g of 97% sulfuric acid as a reagent, 1 35 g of the total amount of the water layer obtained by
Referential Example 1 and 1 80 9 of pure water.
By separating the sulfuric acid layer and the chlorobenzene sulfochloride layer, about 111 5 g of sulfuric acid having a concentration of 73% was recovered from the lower layer. From the upper layer, 286 g of chlorobenzene sulfochloride having a purity of 92% was obtained. The yield based on the fed chlorobenzene was 83%. After the washing with water, 129 9 of the water layer and 277 9 of chlorobenzene sulfochloride having a purity of 95% were obtained.
When compared with Referential Example 2, it is seen that there is no difference in the yield or the purity of the purified chlorobenzene sulfochloride, even when the 60% sulfuric acid containing the water component obtained after the washing with water in Referential Example 1, was used instead of the pure water for the decomposition of the excess chlorosulfonic acid.
Example 9
The operation was carried out in the same manner as in Example 8 except that the chlorobenzene sulfochloride layer separated from the sulfuric acid was mixed with 210 ml of dichloroethane to form a solution.
After the washing with water, 1 29 g of the water layer and 277 g of chlorobenzene sulfochloride having a purity of 95% were obtained.
Example 10 (Recovery and reuse of the effective component from the sulfuric acid layer)
The sulfuric acid layer after separating the chlorobenzene sulfochloride layer in Example 8, was cooled down to 0 C, and the precipitate thereby formed was filtered by means of a centrifugal filtrating machine. As the results, about 1076 g of sulfuric acid having a concentration of 73% and 24 9 of the precipitate were obtained. The precipitate was analyzed and found to contain 71.8% of chlorobenzene sulfonic acid, 13.6% of sulfuric acid and 14.6% of moisture (the "%" is "% by weight").
Twenty four grams of this precipitate (composition: 1 7.2 9 (0.089 mole) of chlorobenzene sulfonic acid, 3.3 g (0.034 mole) of sulfuric acid, and 3.5 9 (0.19 mole) of water) and 53 ml of chlorobenzene were fed into a flask, and distilled under reduced pressure to distil off the chlorobenzene until the boiling point under 100 mmHg became 130"C and to azeotropically remove water. Thereafter, 53 ml of chlorobenzene was again fed and azeotropic dehydration was carried out under the same condition. Then, the solution was diluted with 143 ml of chlorobenzene, whereby 179.7 9 of a homogenous solution of chlorobenzene sulfonic acid was obtained.This homogeneous solution was analyzed and found to contain 18.0 9 (0.093 mole) of chlorobenzene sulfonic acid, 2.9 g (0.030 mole) of sulfuric acid, 0.4 9 (0.024 mole) of water and 1 58.4 g (1.407 moles) of chlorobenzene. It is seen that 0.004 mole of chlorobenzene as the solvent, was fulfonated by sulfuric acid during the azeotropic dehydration. The total amount of the homogeneous solution of the chlorosulfonic acid (chlorobenzene + chlorosulfonic acid
= 1.5 moles) was dropwise added to 524.9 9 (4.5 moles) of chlorosulfonic acid while cooling the system to maintain it at a temperature of at most 60"C. It took about 30 minutes to complete the dropwise addition, and thereafter the system was kept at 60"C for 2 hours.Then, the operation was carried out in the same manner as in Example 8 except that the reaction product thereby obtained, was dropwise added to 788 9 of 60% sulfuric acid prepared from 639 g of the sulfuric acid obtained after separating the precipitate at 0 C, 1 29 9 of the total amount of the water layer obtained after the washing with water in Example 8, and 20 9 of pure water.
By separating the sulfuric acid layer and the chlorobenzene sulfochloride layer, 1083 g of sulfuric acid having a concentration of 74% was recovered from the lower layer. The sulfuric layer was cooled down to 0 C to separate the precipitate, whereupon 36 9 of the precipitate (composition (% by weight): 69.4% of chlorobenzene sulfonic acid, 13.8% of sulfuric acid and 16.8% of moisture) and 1047 9 of sulfuric acid having a concentration of 75% were obtained.
The upper layer was the chlorobenzene sulfochloride layer, from which 290 9 of chlorobenzene sulfochloride having a purity of 92% was obtained. The yield based on the fed chlorobenzene was 90%. After the washing with water, 1 29 9 of the water layer and 281 9 of chlorobenzene sulfochloride having a purity of 95% were obtained.
It is seen the yield of chlorobenzene sulfochloride based on the fed chlorobenzene is higher than that in Example 8.
Claims (10)
1. A process for producing chlorobenzene sulfochloride comprising adding to water or diluted sulfuric acid a reaction mixture of chlorobenzene and chlorosulfonic acid to decompose excess chlorosulfonic acid, driving off remaining hydrogen chloride from the system, bringing the sulfuric acid concentration in the sulfuric acid layer to be from 60 to 90% after completion of the decomposition, and separating chlorobenzene sulfochloride layer; which is characterized in that said chlorobenzene sulfochloride layer is separated in a liquid state at a temperature of from 50 to 80"C.
2. The process as claimed in Claim 1, wherein the separation temperature is from 60 to 75"C.
3. The process as claimed in Claim 1, wherein the decomposition of the chlorosulfonic acid is carried out at a temperature of from 30 to 85"C.
4. The process as claimed in Claim 3, wherein said decomposition is carried out at a temperature of from 40 to 75"C.
5. The process as claimed in Claim 1, which further comprises adding to said chlorobenzene sulfochloride layer an inert organic solvent to prepare a solution; then washing the chlorobenzene sulfochloride with a small amount of water to purify the chlorobenzene sulfochloride; adding afresh to the waste water resultant from said washing, a reaction mixture of chlorobenzene and chlorosulfonic acid to decompose excess chlorosulfonic acid; and further carrying out the separation step.
6. The process as claimed in Claim 1, which further comprises adding to said chlorobenzene sulfochloride layer an inert organic so!vent to prepare a solution; then washing the chlorobenzene sulfochloride with a small amount of water to purify the chlorobenzene sulfochloride; adjusting the diluted sulfuric acid with the waste water resultant from said washing; adding afresh to the diluted sulfuric acid a reaction mixture of chlorobenzene and chlorosulfonic acid to decompose excess chlorosulfonic acid; and further carrying out the separation step.
7. The process as claimed in Claim 5 or 6, wherein said amount of the water to wash the chlorobenzene sulfochloride ranges from 10 to 100 g relative to 100 g of the chlorobenzene sulfochloride layer.
8. The process as claimed in Claim 1, wherein the sulfuric acid layer obtained after completion of the decomposition step is cooled to separate a precipitate, and the precipitate is reused as a feed material to prepare the reaction mixture of chlorobenzene and chlorosulfonic acid.
9. The process as claimed in Claim 1 and substantially as hereinbefore described with reference to Examples 1 to 1 0.
10. Chlorobenzene sulfochloride when produced in a process as claimed in any of the preceding Claims.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55143425A JPS5834469B2 (en) | 1980-10-14 | 1980-10-14 | Method for producing chlorobenzene sulfochloride |
| JP16074380A JPS6034946B2 (en) | 1980-11-17 | 1980-11-17 | Method for producing chlorobenzene sulfochloride |
| JP7874381A JPS6035340B2 (en) | 1981-05-26 | 1981-05-26 | Method for producing chlorobenzene sulfochloride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2087386A true GB2087386A (en) | 1982-05-26 |
| GB2087386B GB2087386B (en) | 1984-09-12 |
Family
ID=27302799
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8130118A Expired GB2087386B (en) | 1980-10-14 | 1981-10-06 | Process for producing chlorobenzene sulfochloride |
Country Status (3)
| Country | Link |
|---|---|
| DE (1) | DE3140854A1 (en) |
| FR (1) | FR2491923A1 (en) |
| GB (1) | GB2087386B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3302647A1 (en) * | 1983-01-27 | 1984-08-02 | Hoechst Ag, 6230 Frankfurt | METHOD FOR PRODUCING 4-CHLORPHENYLSULFONYL COMPOUNDS |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3108137A (en) * | 1959-08-31 | 1963-10-22 | Chemetron Corp | Production of organic sulfonyl chlorides |
| GB1007655A (en) * | 1962-02-19 | 1965-10-13 | Konink Zwavelzuurfabrieken V H | Process for the manufacture of organic sulphonylchlorides |
| US3632642A (en) * | 1968-10-07 | 1972-01-04 | Chris Craft Ind Inc | Production of arylsulfonyl chlorides |
-
1981
- 1981-10-06 GB GB8130118A patent/GB2087386B/en not_active Expired
- 1981-10-14 FR FR8119353A patent/FR2491923A1/en active Granted
- 1981-10-14 DE DE19813140854 patent/DE3140854A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| DE3140854A1 (en) | 1982-05-27 |
| FR2491923B1 (en) | 1985-03-15 |
| FR2491923A1 (en) | 1982-04-16 |
| GB2087386B (en) | 1984-09-12 |
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| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |