CN116751141A - Preparation method of p-chlorobenzenesulfonyl chloride and preparation method of 4,4' -dichlorodiphenyl sulfone - Google Patents
Preparation method of p-chlorobenzenesulfonyl chloride and preparation method of 4,4' -dichlorodiphenyl sulfone Download PDFInfo
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- CN116751141A CN116751141A CN202310752722.1A CN202310752722A CN116751141A CN 116751141 A CN116751141 A CN 116751141A CN 202310752722 A CN202310752722 A CN 202310752722A CN 116751141 A CN116751141 A CN 116751141A
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- chlorobenzenesulfonyl chloride
- chlorobenzene
- chloride
- chlorobenzenesulfonyl
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- ZLYBFBAHAQEEQQ-UHFFFAOYSA-N 4-chlorobenzenesulfonyl chloride Chemical compound ClC1=CC=C(S(Cl)(=O)=O)C=C1 ZLYBFBAHAQEEQQ-UHFFFAOYSA-N 0.000 title claims abstract description 64
- GPAPPPVRLPGFEQ-UHFFFAOYSA-N 4,4'-dichlorodiphenyl sulfone Chemical compound C1=CC(Cl)=CC=C1S(=O)(=O)C1=CC=C(Cl)C=C1 GPAPPPVRLPGFEQ-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims abstract description 103
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 51
- 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 42
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 230000007062 hydrolysis Effects 0.000 claims abstract description 11
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 11
- 238000004821 distillation Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000000605 extraction Methods 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 238000001953 recrystallisation Methods 0.000 claims abstract description 4
- 238000000926 separation method Methods 0.000 claims abstract description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 34
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 30
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 239000012043 crude product Substances 0.000 description 37
- 239000007789 gas Substances 0.000 description 23
- 238000002474 experimental method Methods 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 16
- KMVZDSQHLDGKGV-UHFFFAOYSA-N 2-chlorobenzenesulfonyl chloride Chemical compound ClC1=CC=CC=C1S(Cl)(=O)=O KMVZDSQHLDGKGV-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 8
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000004817 gas chromatography Methods 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000002699 waste material Substances 0.000 description 7
- YKWDWSGYZBURDA-UHFFFAOYSA-N 1-chloro-2-(4-chlorophenyl)sulfonylbenzene Chemical compound C1=CC(Cl)=CC=C1S(=O)(=O)C1=CC=CC=C1Cl YKWDWSGYZBURDA-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- RJWBTWIBUIGANW-UHFFFAOYSA-N 4-chlorobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(Cl)C=C1 RJWBTWIBUIGANW-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- RKIDDEGICSMIJA-UHFFFAOYSA-N 4-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=C(Cl)C=C1 RKIDDEGICSMIJA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 239000002351 wastewater 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of p-chlorobenzenesulfonyl chloride and a preparation method of 4,4' -dichlorodiphenyl sulfone, and relates to the technical field of preparation methods of p-chlorobenzenesulfonyl chloride, wherein chlorobenzene and chlorosulfonic acid react for a first preset time at a first preset temperature to obtain an intermediate 1; the intermediate 1 reacts for a second preset time under the action of thionyl chloride at a second preset temperature to obtain a mixed solution containing p-chlorobenzenesulfonyl chloride, and then the mixed solution containing p-chlorobenzenesulfonyl chloride is subjected to extraction, hydrolysis, liquid separation, washing, distillation and recrystallization to obtain the p-chlorobenzenesulfonyl chloride.
Description
Technical Field
The invention belongs to the technical field of p-chlorobenzenesulfonyl chloride preparation methods, and particularly relates to a preparation method of p-chlorobenzenesulfonyl chloride and a preparation method of 4,4' -dichloro diphenyl sulfone.
Background
The p-chlorobenzenesulfonyl chloride is white prismatic crystal, is an intermediate for synthesizing medicines, and is mainly used for producing medicines such as Taier, 4' -dichloro diphenyl sulfone and the like. The traditional production process for synthesizing the p-chlorobenzenesulfonyl chloride is various, and the industrial production at home and abroad mainly adopts an excessive chlorosulfonic acid method and a sulfur trioxide method. The chlorosulfonic acid method has the advantages of mature production process, good product quality, complex process, high equipment requirement, more acid wastewater generation and environmental harm. The sulfur trioxide method is to add sulfur trioxide into chlorobenzene to carry out sulfonation reaction, and dimethyl sulfoxide is adopted, so that the product prepared by the method has good quality, high yield, mild reaction conditions and low equipment requirements, but the flow and concentration of the sulfur trioxide in the reaction process are difficult to control, and the tail gas pollution is serious.
In the prior art, as disclosed in the Chinese patent application No. 201110246016.7, an improved chlorosulfonation method of 4,4' -dichlorodiphenyl sulfone is disclosed, which comprises the following steps: chlorobenzene and chlorosulfonic acid are used as reaction raw materials, dichloromethane is used as a solvent for reaction, then solid sodium chloride is added to prepare p-chlorobenzenesulfonyl chloride, and the sodium chloride is added to improve the preparation efficiency of the p-chlorobenzenesulfonyl chloride, but the product purity is low.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing p-chlorobenzenesulfonyl chloride with improved purity
Also provides a preparation method of the 4,4' -dichlorodiphenyl sulfone.
The technical scheme adopted for solving the technical problems is as follows:
a preparation method of p-chlorobenzenesulfonyl chloride comprises the following steps:
s1: chlorobenzene and chlorosulfonic acid react for a first preset time at a first preset temperature to obtain an intermediate 1;
s2: the intermediate 1 reacts for a second preset time at a second preset temperature under the action of thionyl chloride to obtain a mixed solution containing p-chlorobenzenesulfonyl chloride, and then the mixed solution containing p-chlorobenzenesulfonyl chloride is subjected to extraction, hydrolysis, liquid separation, washing, distillation and recrystallization to obtain the p-chlorobenzenesulfonyl chloride.
Preferably, in the step S1, the chlorosulfonic acid is added dropwise to the chlorobenzene.
Preferably, in the step S1, the chlorobenzene is added dropwise to the chlorosulfonic acid.
Preferably, the first temperature is 5-45 ℃, the first preset time is 1-2 h, the second preset temperature is 45-65 ℃, and the second preset time is 1-5 h.
Preferably, the molar ratio of the thionyl chloride to the chlorobenzene is 1:2-5.
Preferably, in the step S2, the thionyl chloride is added after the intermediate 1 is reacted at the second predetermined temperature for 0.5h to 1.5 h.
Preferably, the molar ratio of chlorosulfonic acid to chlorobenzene is 2-5:1.
Preferably, in the step S2, the extracting step is to add chloroform as an extractant into the mixed solution containing p-chlorobenzenesulfonyl chloride to extract, thereby obtaining an extract.
Preferably, in the step S2, the hydrolysis is specifically: hydrochloric acid is added to the extract to hydrolyze the excess chlorosulfonic acid.
A process for the preparation of 4,4' -dichlorodiphenyl sulfone comprising the process for the preparation of p-chlorobenzenesulfonyl chloride as described above.
Compared with the prior art, the invention has the beneficial effects that:
the intermediate 1 is obtained by reacting for a preset time at a first preset temperature, then the intermediate 1 generates gas under the action of thionyl chloride, and after the gas is released, the reaction of the intermediate 1 and chlorobenzene is promoted to be carried out forward, so that the utilization rate of the chlorobenzene reaches 90%, and the purity of the product reaches 99%.
Drawings
FIG. 1 is a gas chromatogram of experiment No. 1 of example one.
Fig. 2 is a gas chromatogram of experiment No. 2 of example one.
FIG. 3 is a gas chromatogram of experiment No. 3 of example one.
Fig. 4 is a gas chromatogram of experiment No. 4 of example one.
Fig. 5 is a gas chromatogram of experiment No. 5 of example one.
FIG. 6 is a gas chromatogram of experiment No. 6 of example one.
FIG. 7 is a gas chromatogram after distillation under reduced pressure according to example I.
FIG. 8 is a gas chromatogram after purification of example one 4,4' -dichlorodiphenyl sulfone.
Fig. 9 is a gas chromatogram of experiment No. 7 of example two.
FIG. 10 is a gas chromatogram of experiment No. 8 of example two.
Fig. 11 is a gas chromatogram of experiment No. 9 of example two.
Detailed Description
The technical scheme and technical effects of the embodiments of the present invention are further described in detail below with reference to the accompanying drawings.
A preparation method of p-chlorobenzenesulfonyl chloride comprises the following steps:
s1: chlorobenzene and chlorosulfonic acid react for a first preset time at a first preset temperature to obtain an intermediate 1;
s2: the intermediate 1 reacts for a second preset time at a second preset temperature under the action of thionyl chloride to obtain a mixed solution containing p-chlorobenzenesulfonyl chloride, and then the mixed solution containing p-chlorobenzenesulfonyl chloride is subjected to extraction, hydrolysis, liquid separation, washing, distillation and recrystallization to obtain the p-chlorobenzenesulfonyl chloride.
Compared with the prior art, the invention has the beneficial effects that:
the intermediate 1 is obtained by reacting for a preset time at a first preset temperature, then the intermediate 1 generates gas under the action of thionyl chloride, and after the gas is released, the reaction of the intermediate 1 and chlorobenzene is promoted to be carried out forward, so that the utilization rate of the chlorobenzene is more than 90%, and the purity of the product is 99%.
Further, in the step S1, the chlorosulfonic acid is added dropwise to the chlorobenzene, the yield of p-chlorobenzenesulfonyl chloride is high, and a small amount of by-product 4,4' -dichlorodiphenyl sulfone is produced.
Further, in S1, the chlorobenzene is added dropwise to the chlorosulfonic acid, so that intermediate 1 is produced highly, and the yield of p-chlorobenzenesulfonyl chloride is high.
Further, the first predetermined temperature is 5 ℃ to 45 ℃, preferably 30 ℃ to 35 ℃, the first predetermined time is 1h to 2h, the para position is positioned at 30 ℃ to 35 ℃ under exothermic reaction of the intermediate 1, the generation of ortho-position products is restrained, the generated para-position intermediate 1 is further reduced, the second predetermined temperature is 45 ℃ to 65 ℃, preferably 50 ℃ to 55 ℃, the second predetermined time is 1h to 5h, preferably 2.5h to 3.5h, and the intermediate 1 is further reacted with chlorosulfonic acid to generate p-chlorobenzenesulfonyl chloride.
Furthermore, the mol ratio of the thionyl chloride to the chlorobenzene is 1:2-5, when the thionyl chloride is not added, the reaction of the intermediate 1 and chlorosulfonic acid reaches equilibrium, the thionyl chloride is added, the activity of the thionyl chloride is stronger than that of the chlorosulfonic acid, the equilibrium is broken, the thionyl chloride reacts with the intermediate 1 to generate p-chlorobenzenesulfonyl chloride and gas under the participation of the thionyl chloride, the reaction is promoted to be carried out forward after the gas is released, because the intermediate 1 can be separated out at low temperature, a pipeline is blocked, the intermediate 1 in waste acid is reduced after the residual intermediate 1 is reacted by the thionyl chloride, and the waste acid treatment is smoother.
In the step S2, the thionyl chloride is added after the intermediate 1 reacts for 0.5h to 1.5h at the second preset temperature, and is added after the intermediate 1 and chlorosulfonic acid react to reach equilibrium.
Further, the molar ratio of chlorosulfonic acid to chlorobenzene is 2-5:1, preferably 2-3:1.
in the step S2, chloroform as an extractant is added to the mixed solution containing p-chlorobenzenesulfonyl chloride to extract the mixed solution to obtain an extract.
Further, in S2, the hydrolysis specifically includes: and adding hydrochloric acid into the extract to hydrolyze excessive chlorosulfonic acid, wherein the hydrochloric acid is 30% hydrochloric acid, water in the hydrochloric acid reacts with unreacted chlorosulfonic acid to generate hydrogen chloride and sulfuric acid, the reaction releases heat, and in order to prevent local release of heat, the hydrolysis of p-chlorobenzenesulfonyl chloride is caused to generate an intermediate 1, and the generated hydrogen chloride gas brings out the heat of the reaction, so that the yield of the p-chlorobenzenesulfonyl chloride is not influenced.
Example one (chlorobenzene was added dropwise to chlorosulfonic acid):
adding chlorosulfonic acid into a four-neck flask with a stirrer, a reflux and gas absorption device and a thermometer, and dripping 0.5mol of chlorobenzene through a constant-pressure dropping funnel at the temperature of 6-12 ℃; the dripping time is 1h, and the temperature is kept for 30min at 6-12 ℃ after the dripping is finished; then heating to 50-55 ℃, and preserving heat for 1h; then 0.25mol of sulfoxide chloride is added through a dropping funnel, and after the addition is completed for 10 minutes, the temperature is kept at 50-55 ℃ for 3 hours; cooling to room temperature, and adding 150ml of chloroform; 35ml of 30% hydrochloric acid solution is gradually added dropwise through a dropping funnel to decompose excessive chlorosulfonic acid; separating, treating the acid layer with waste acid, and washing the chloroform layer with distilled water once; the chloroform layer after washing was distilled off at normal pressure to remove most of chloroform, and then residual chloroform was distilled off under reduced pressure with a water pump to obtain a crude product, which was sampled for GC analysis.
According to the above experimental method, a method for improving the yield of p-chlorobenzenesulfonyl chloride was investigated.
1. Control groups of 3 were set, 1mol, 1.25mol, 1.5mol chlorosulfonic acid, numbered 1-3, were added respectively, and the results are shown in Table 1 by GC analysis in the same manner as in example one above.
TABLE 1
| Experiment number | 1 | 2 | 3 |
| Chlorosulfonic acid to chlorobenzene molar ratio | 2:1 | 2.5:1 | 3:1 |
| Yield g | 87.3 | 92.1 | 92.7 |
| Chlorobenzene utilization/% | 88.02 | 93.31 | 91.51 |
| The ratio of chlorobenzene in the crude product/% | 1.63 | 0.96 | 0.19 |
| P-chlorobenzenesulfonyl chloride in crude product | 79.47 | 79.96 | 88.44 |
| The ratio of O-chlorobenzenesulfonyl chloride in the crude product/% | 1.57 | 2.06 | 2.25 |
| The ratio of 4,4' -dichloro diphenyl sulfone in the crude product/% | 17.13 | 16.92 | 9.09 |
| The ratio of 2,4' -dichloro diphenyl sulfone in the crude product/% | 0.19 | 0.08 | 0.02 |
From the above results, it was found that the higher the yield of p-chlorobenzenesulfonyl chloride produced in the crude product was, the higher the molar ratio of chlorosulfonic acid to chlorobenzene was, the higher the p-chlorobenzenesulfonyl chloride produced in the crude product was 88.44% when the molar ratio of chlorosulfonic acid to chlorobenzene was 3:1, and the o-chlorobenzenesulfonyl chloride, 4' -dichlorodiphenyl sulfone was only 2.25%, 9.09%, and the chlorobenzene utilization rate was 91.51%.
When 4,4' -dichlorodiphenyl sulfone is produced by p-chlorobenzenesulfonyl chloride, the molar ratio of chlorosulfonic acid to chlorobenzene is most preferably 2.5:1, 16.92% of 4,4' -dichlorodiphenyl sulfone is already produced when p-chlorobenzenesulfonyl chloride is produced, and the ratio of o-chlorobenzenesulfonyl chloride to 2,4' -dichlorodiphenyl sulfone is small.
2. The control group 1 was set at a first predetermined temperature (temperature at which chlorobenzene was added dropwise) of 30℃to 35℃and No. 4, and the results of GC analysis, as shown in FIG. 4, are shown in Table 2, in the same manner as in the step of reference numeral 2.
TABLE 2
| Experiment number | 2 | 4 |
| A first predetermined temperature | 10℃-20℃ | 30℃-35℃ |
| Yield g | 92.1 | 91.6 |
| Chlorobenzene utilization/% | 93.31 | 91.52 |
| The ratio of chlorobenzene in the crude product/% | 0.96 | 0.04 |
| P-chlorobenzenesulfonyl chloride in crude product | 79.96 | 86.63 |
| The ratio of O-chlorobenzenesulfonyl chloride in the crude product/% | 2.06 | 1.87 |
| The ratio of 4,4' -dichloro diphenyl sulfone in the crude product/% | 16.92 | 11.41 |
| The ratio of 2,4' -dichloro diphenyl sulfone in the crude product/% | 0.08 | 0.05 |
From the above results, it is apparent that when chlorosulfonic acid reacts with chlorobenzene, the content of p-chlorobenzenesulfonyl chloride is significantly increased and the content of 4,4' -dichlorodiphenyl sulfone is reduced when the first predetermined temperature is increased, which is advantageous for the production of p-chlorobenzenesulfonyl chloride.
3. Control 1 was set, hydrolyzed using water in the hydrolysis step, hydrolyzed using no 30% hydrochloric acid, no. 5, and analyzed by GC as in step 2, as shown in fig. 5, and the results are shown in table 3.
TABLE 3 Table 3
From the above results, it was found that, in the case of reacting chlorosulfonic acid with chlorobenzene, hydrolysis using pure water was hardly different from hydrolysis using 30% hydrochloric acid; the main function of the hydrochloric acid is that the heat generated by the reaction is taken away by hydrogen chloride gas, and in the subsequent waste acid treatment process, the waste acid mainly comprises sulfuric acid (concentration is 75-80%) and p-chlorobenzenesulfonic acid, and the p-chlorobenzenesulfonic acid with a certain concentration can be separated out of a concentrated sulfuric acid solution at a low temperature, so that the solid is difficult to separate out and is easy to cause pipeline blockage; on the one hand, 30% hydrochloric acid takes away local heat through hydrogen chloride to prevent generated p-chlorobenzenesulfonyl chloride from being dissolved, and on the other hand, 30% hydrochloric acid dissolves chlorosulfonic acid, so that a pipeline is unobstructed when waste acid is treated.
4. Control 1 was set up, no thionyl chloride was added to the reaction, and GC analysis was performed in the same manner as in number 6, the other steps in number 2, as shown in fig. 6, and the results are shown in table 4.
TABLE 4 Table 4
| Experiment number | 2 | 6 |
| With or without addition of thionyl chloride | Has the following components | Without any means for |
| Yield g | 92.1 | 82.43 |
| Chlorobenzene utilization/% | 93.31 | 85.51 |
| The ratio of chlorobenzene in the crude product/% | 0.96 | 0.09 |
| P-chlorobenzenesulfonyl chloride in crude product | 79.96 | 78.58 |
| The ratio of O-chlorobenzenesulfonyl chloride in the crude product/% | 2.06 | 1.19 |
| The ratio of 4,4' -dichloro diphenyl sulfone in the crude product/% | 16.92 | 19.99 |
| The ratio of 2,4' -dichloro diphenyl sulfone in the crude product/% | 0.08 | 0.15 |
From the above results, when the equivalent of chlorosulfonic acid cannot affect the p-chlorobenzenesulfonyl chloride ratio in the crude product, and thionyl chloride is not added in the reaction, the utilization rate of chlorobenzene is reduced although the p-chlorobenzenesulfonyl chloride ratio in the crude product is also very high, so that the use efficiency of chlorobenzene is reduced, and therefore, thionyl chloride can improve the use efficiency of chlorobenzene, reduce the production cost and facilitate the generation of 4,4' -dichlorodiphenyl sulfone.
Carrying out reduced pressure distillation on the crude product, wherein the distillate is a mixture of p-chlorobenzenesulfonyl chloride and o-chlorobenzenesulfonyl chloride; the distillation residue mainly contains 4,4' -dichloro diphenyl sulfone, the mixture of p-chlorobenzene sulfonyl chloride and o-chlorobenzene sulfonyl chloride is mixed and dissolved with a proper amount of chloroform at 55 ℃, the mixture is stirred and cooled for crystallization to obtain solid, and the obtained crystal is subjected to suction filtration and is analyzed by GC, as shown in figure 7, and the following results are obtained: the crystal contains more than 99 percent of p-chlorobenzenesulfonyl chloride, and the purity is suitable for synthesizing 4,4' -dichlorodiphenyl sulfone; while the ortho-isomer remains in the mother liquor.
4,4' -dichlorodiphenyl sulfone purification in the distillation residue: a) Alkali treatment: grinding the distillation residue crude product into fine particles, transferring into hot 10% liquid alkali for treatment (50 ℃ for 30 min), adding chloroform for dissolving, stirring at 50 ℃ for 30min, separating to obtain an organic layer, and discarding a water layer; b) Concentrating and crystallizing: concentrating the organic layer at 70 ℃ to remove most of chloroform, cooling for crystallization, and carrying out suction filtration to obtain crystals, wherein mother liquor is used for the next crude product treatment; c) And (5) recrystallizing: redissolving the crystals at 50:50 Adding 0.5% active carbon into the chloroform/ethanol mixed solvent of (v/v), further decolorizing at 50deg.C, filtering while the filtrate is hot, cooling the filtrate to 5deg.C, centrifuging, and drying to obtain crystal 4,4' -dichlorodiphenyl sulfone, and detecting product purity, wherein the gas chromatogram is shown in figure 8, and the purity reaches over 99.5%.
Example di (chlorosulfonic acid drop wise to chlorobenzene):
1. adding 0.5mol of chlorobenzene into a four-neck flask provided with a stirrer, a reflux and gas absorption device and a thermometer, starting to dropwise add 1.25mol of chlorosulfonic acid through a constant pressure dropping funnel at the temperature of 6-12 ℃, wherein the dropwise adding time is 1h, and preserving heat for 30min at the temperature of 6-12 ℃ after the dropwise adding is finished; then heating to 50-55 ℃ and preserving heat for 3h; cooling to room temperature, and adding 150ml of chloroform; through the dropping funnel, 32ml of 30% hydrochloric acid solution is gradually added dropwise to decompose excessive chlorosulfonic acid; separating, treating the acid layer with waste acid, and washing the chloroform layer with distilled water once; the chloroform layer after washing was distilled off under normal pressure to remove most of chloroform, and then residual chloroform was distilled off under reduced pressure with a water pump to obtain a crude product, which was sampled for GC analysis, as shown in FIG. 9, and the results are shown in Table 5, experiment No. 7, and the crude product purification step was the same as in example one.
TABLE 5
As can be seen from comparison of experiment 2 and experiment 7, p-chlorobenzoyl chloride can be generated regardless of the addition, but chlorosulfonic acid is added dropwise to chlorobenzene, the chlorobenzene utilization rate is improved to 96.68%, but the content of p-chlorobenzenesulfonyl chloride in the crude product is reduced to 66.71%, the content of o-chlorobenzenesulfonyl chloride in the crude product is reduced to 0.89%, and 32.04% of 4,4' -dichlorodiphenyl sulfone is generated, and chlorosulfonic acid is added dropwise to chlorobenzene when 4,4' -dichlorodiphenyl sulfone is directly prepared by the reaction, so that the generation of 4,4' -dichlorodiphenyl sulfone is facilitated.
2. 1 control group was set, at a first predetermined temperature (temperature at which chlorosulfonic acid was added dropwise) of 30℃to 35℃and No. 8, and the results were shown in Table 6, as shown in FIG. 10, by GC analysis in the same manner as in the step of reference numeral 7.
TABLE 6
| Experiment number | 7 | 8 |
| A first predetermined temperature | 10℃-20℃ | 30℃-35℃ |
| Yield g | 88.6 | 90.14 |
| Chlorobenzene utilization/% | 96.68 | 97.4 |
| The ratio of chlorobenzene in the crude product/% | 0.11 | 0.09 |
| P-chlorobenzenesulfonyl chloride in crude product | 66.71 | 68.79 |
| The ratio of O-chlorobenzenesulfonyl chloride in the crude product/% | 0.89 | 1.25 |
| The ratio of 4,4' -dichloro diphenyl sulfone in the crude product/% | 32.04 | 29.28 |
| The ratio of 2,4' -dichloro diphenyl sulfone in the crude product/% | 0.24 | 0.58 |
From the above results, it is found that raising the first predetermined temperature can increase the chlorobenzene utilization, resulting in a reduction in production cost.
3. Control 1 was set up, no thionyl chloride was added to the reaction, and GC analysis was performed in the same manner as in number 9, the other steps described in number 7, as shown in fig. 11, and the results are shown in table 7.
TABLE 7
| Experiment number | 7 | 9 |
| With or without addition of thionyl chloride | Has the following components | Without any means for |
| Yield g | 88.6 | 79.3 |
| Chlorobenzene utilization/% | 96.68 | 87.29 |
| The ratio of chlorobenzene in the crude product/% | 0.11 | 0.12 |
| P-chlorobenzenesulfonyl chloride in crude product | 66.71 | 65.12 |
| The ratio of O-chlorobenzenesulfonyl chloride in the crude product/% | 0.89 | 0.33 |
| The ratio of 4,4' -dichloro diphenyl sulfone in the crude product/% | 32.04 | 33.96 |
| The ratio of 2,4' -dichloro diphenyl sulfone in the crude product/% | 0.24 | 0.47 |
From the above results, it is clear that thionyl chloride can improve the efficiency of chlorobenzene use and reduce the production cost.
The foregoing disclosure is illustrative of the preferred embodiments of the present invention, and is not to be construed as limiting the scope of the invention, as it is understood by those skilled in the art that all or part of the above-described embodiments may be practiced with equivalents thereof, which fall within the scope of the invention as defined by the appended claims.
Claims (10)
1. A preparation method of p-chlorobenzenesulfonyl chloride is characterized by comprising the following steps of: the method comprises the following steps:
s1: chlorobenzene and chlorosulfonic acid react for a first preset time at a first preset temperature to obtain an intermediate 1;
s2: the intermediate 1 reacts for a second preset time at a second preset temperature under the catalysis of thionyl chloride to obtain a mixed solution containing p-chlorobenzenesulfonyl chloride, and then the mixed solution containing p-chlorobenzenesulfonyl chloride is subjected to extraction, hydrolysis, liquid separation, washing, distillation and recrystallization to obtain the p-chlorobenzenesulfonyl chloride.
2. The process for preparing p-chlorobenzenesulfonyl chloride according to claim 1, wherein: in the step S1, the chlorosulfonic acid is added dropwise to the chlorobenzene.
3. The process for preparing p-chlorobenzenesulfonyl chloride according to claim 1, wherein: in the step S1, the chlorobenzene is added dropwise to the chlorosulfonic acid.
4. The process for preparing p-chlorobenzenesulfonyl chloride according to claim 1, wherein: the first temperature is 5-45 ℃, the first preset time is 1-2 h, the second preset temperature is 45-65 ℃, and the second preset time is 1-5 h.
5. The process for preparing p-chlorobenzenesulfonyl chloride according to claim 1, wherein: the molar ratio of the thionyl chloride to the chlorobenzene is 1:2-5.
6. The process for preparing p-chlorobenzenesulfonyl chloride according to claim 5, wherein: in the step S2, the thionyl chloride is added after the intermediate 1 reacts for 0.5h to 1.5h at a second preset temperature.
7. The process for preparing p-chlorobenzenesulfonyl chloride according to claim 1, wherein: the mol ratio of chlorosulfonic acid to chlorobenzene is 2-5:1.
8. the process for preparing p-chlorobenzenesulfonyl chloride according to claim 1, wherein: in the step S2, the extraction step is to add chloroform as an extractant into the mixed solution containing the p-chlorobenzenesulfonyl chloride for extraction to obtain an extract.
9. The process for preparing p-chlorobenzenesulfonyl chloride according to claim 8, wherein: in the step S2, the hydrolysis is specifically: hydrochloric acid is added to the extract to hydrolyze the excess chlorosulfonic acid.
10. A preparation method of 4,4' -dichloro diphenyl sulfone is characterized in that: a process for the preparation of p-chlorobenzenesulfonyl chloride comprising any one of claims 1 to 9.
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