CN113880736A - Preparation method of 4, 4' -dimethyl diphenyl sulfone - Google Patents
Preparation method of 4, 4' -dimethyl diphenyl sulfone Download PDFInfo
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- CN113880736A CN113880736A CN202111493217.7A CN202111493217A CN113880736A CN 113880736 A CN113880736 A CN 113880736A CN 202111493217 A CN202111493217 A CN 202111493217A CN 113880736 A CN113880736 A CN 113880736A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/06—Separation; Purification; Stabilisation; Use of additives
Abstract
The invention belongs to the technical field of chemical production, and particularly relates to a preparation method of 4, 4' -dimethyl diphenyl sulfone, which comprises the following steps: (1) condensation reaction; mixing p-toluenesulfonyl chloride with a catalyst, and dropwise adding toluene at the temperature of 90-120 ℃ to perform condensation reaction; (2) hydrolysis: hydrolyzing a small amount of incompletely reacted p-toluenesulfonyl chloride; (3) and (5) refining. The reaction raw materials of the invention are paratoluensulfonyl chloride and toluene, the raw materials have wide sources and low price, and the refined product has high content which can reach more than 99 percent; the centrifugal mother liquor (ferric trichloride aqueous solution) can be reused as a flocculation water purifier for sewage treatment, has no solid waste and no waste water, and has the advantages of environment-friendly process, short condensation reaction time, high yield and yield of over 98 percent.
Description
Technical Field
The invention belongs to the technical field of chemical production, and particularly relates to a preparation method of 4, 4' -dimethyl diphenyl sulfone.
Background
4,4 '-dimethyl diphenyl sulfone is an important organic chemical intermediate, can be used for preparing 4, 4' -dicarboxyl diphenyl sulfone and organic synthesis, and is used as a plasticizer in the production process of high molecular materials, plastics, rubber, adhesives, cellulose, resins, medical instruments and cables so as to improve the plasticity and flexibility of the materials.
At present, no report of the production process is found in China.
Disclosure of Invention
The invention aims to provide a preparation method of 4, 4' -dimethyl diphenyl sulfone, which has the advantages of short reaction time, high yield and stable product quality, and aims to solve the problems in the background technology.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
a preparation method of 4, 4' -dimethyl diphenyl sulfone comprises the following steps:
(1) condensation reaction; mixing paratoluensulfonyl chloride with a catalyst, heating, dripping toluene at 90-120 ℃, keeping the temperature at 120-130 ℃ after finishing dripping, and carrying out heat preservation reaction for 2-5 hours under the micro-negative pressure;
(2) hydrolysis: after the condensation reaction is finished, hydrolyzing incompletely reacted p-toluenesulfonyl chloride at 20-90 ℃, cooling and centrifuging after the hydrolysis is finished to obtain a 4, 4' -dimethyl diphenyl sulfone crude product and a centrifugal mother solution;
(3) refining: and (3) dissolving the 4,4 '-dimethyl diphenyl sulfone crude product by adding a solvent, cooling, recrystallizing and filtering to obtain a 4, 4' -dimethyl diphenyl sulfone refined product.
Condensation reaction:
the condensation reaction is carried out under micro negative pressure, the generated hydrogen chloride gas can be discharged out of the system in time, the reaction is promoted to be carried out in the positive direction, the generated gas is discharged in time, positive pressure cannot be formed in the equipment, and the process safety is ensured.
The reaction activity of the p-toluenesulfonyl chloride and toluene is low, so high temperature is needed, a catalyst is added, and a small amount of p-toluenesulfonyl chloride cannot completely react during the reaction; the raw material p-toluenesulfonyl chloride has odor, and the presence of a small amount of the raw material causes the product to have odor, so that hydrolysis is needed to completely react the p-toluenesulfonyl chloride.
As an improvement, in the step (1), the catalyst is ferric trichloride.
As an improvement, in the step (2), the temperature is reduced to below 40 ℃.
As an improvement, in the step (3), the solvent is dichloromethane, dichloroethane, methanol or ethanol.
Preferably, the solvent is dichloromethane.
As an improvement, in the step (3), the temperature is raised to 40 ℃ when the solvent is added for dissolution.
As an improvement, in the step (3), the temperature is reduced to 5-10 ℃.
Due to the adoption of the technical scheme, the invention has the beneficial effects that:
according to the preparation method provided by the invention, reaction raw materials are p-toluenesulfonyl chloride and toluene, the raw materials are wide in source and low in price, the content of the refined product is high, and the content of the product can reach more than 99%; the centrifugal mother liquor (ferric trichloride aqueous solution) can be reused as a flocculation water purifier for sewage treatment, has no solid waste and no waste water, and has the advantages of environment-friendly process, short condensation reaction time, high yield and yield of over 98 percent.
Drawings
FIG. 1 is a process flow diagram provided by the present invention.
Detailed Description
The present invention will be further described with reference to the following detailed description and accompanying drawings.
Example 1
Adding 95.8g (the content is 99.5 percent, 0.5 mol) of paratoluensulfonyl chloride and 4.5g of ferric trichloride into a 500ml four-product bottle, heating the mixture in an oil bath kettle, stirring and heating the mixture to 90 ℃, adding 48.4g (the content is 99.95 percent, and the content is 5 percent excessive) of toluene into a constant-pressure dropping funnel, starting to drop toluene, dropping the toluene for about 1 hour until the dropping process is finished, slowly raising the temperature to 95 ℃ in the dropping process, keeping the temperature at 120 ℃ for reaction for 3 hours, keeping the reaction pressure at-0.005 MPa, sampling and detecting that the raw materials are completely reacted, cooling the temperature to 60 ℃, adding 20ml of water for hydrolysis, obtaining a 4,4 '-dimethyl diphenyl sulfone crude product and a centrifugal mother liquor (an iron trichloride aqueous solution), continuously cooling the temperature to below 40 ℃ after hydrolysis, adding 240 g of dichloromethane into the 4, 4' -dimethyl diphenyl sulfone crude product, stirring and heating the temperature to 40 ℃, adding an ice brine bath, cooling the temperature to 5 ℃, precipitating crystals, suction filtering, and filtering, Drying to obtain 122.45 g of 4, 4' -dimethyl diphenyl sulfone, the detection content is 99.52 percent, and the experimental yield is 99.05 percent.
Example 2
Adding 95.8g (content: 99.5%, 0.5 mol) of p-toluenesulfonyl chloride and 4.5g of ferric trichloride into a 500ml four-product bottle, heating in an oil bath kettle, stirring and heating to 90 ℃, adding 48.4g (toluene content: 99.95%, excessive 5 wt%) of toluene into a constant-pressure dropping funnel, starting to drop toluene, dropping for about 1 hour until the dropping process temperature is slowly increased to 105 ℃, keeping at 125 ℃ for reaction for 3 hours, keeping the reaction pressure at-0.01 MPa, sampling and detecting that the raw materials are completely reacted, cooling to 60 ℃, adding 20ml of water for hydrolysis, hydrolyzing at 20 ℃, centrifuging to obtain a 4,4 '-dimethyldiphenylsulfone crude product and a centrifugal mother liquor (ferric trichloride aqueous solution), continuously cooling to below 40 ℃ after hydrolysis, adding 240 g of dichloromethane into the 4, 4' -dimethyldiphenylsulfone crude product, stirring and heating to 40 ℃ for dissolution, adding an ice brine bath, cooling to 7 ℃, precipitating crystals, suction filtering, and vacuum-filtering, Drying to obtain 122.53 g of 4, 4' -dimethyl diphenyl sulfone, the detection content is 99.56%, and the experimental yield is 99.15%.
Example 3
Adding 95.8g (content: 99.5%, 0.5 mol) of p-toluenesulfonyl chloride and 4.5g of ferric trichloride into a 500ml four-product bottle, heating in an oil bath kettle, stirring and heating to 90 ℃, adding 48.4g (toluene content: 99.95%, excessive 5 wt%) of toluene into a constant-pressure dropping funnel, starting to drop toluene, dropping for about 1 hour until the dropping process temperature is slowly increased to 115 ℃, keeping at 130 ℃ for reaction for 2 hours, the reaction pressure is-0.012 MPa, sampling and detecting that the raw materials are completely reacted, cooling to 60 ℃, adding 20ml of water for hydrolysis, the hydrolysis temperature is 70 ℃, centrifuging to obtain a 4,4 '-dimethyl diphenyl sulfone crude product and a centrifugal mother liquor (ferric trichloride aqueous solution), continuously cooling to below 40 ℃ after hydrolysis, adding 240 g of dichloromethane into the 4, 4' -dimethyl diphenyl sulfone crude product, stirring and heating to 40 ℃ for dissolution, adding an ice brine bath, cooling to 6 ℃, precipitating crystals, suction filtering, and vacuum-filtering, Drying to obtain 122.58 g of 4, 4' -dimethyl diphenyl sulfone, the detection content is 99.53 percent, and the experimental yield is 99.16 percent.
Example 4
Adding 95.8g (the content is 99.5 percent and 0.5 mol) of paratoluensulfonyl chloride and 4.5g of ferric trichloride into a 500ml four-product bottle, heating the mixture in an oil bath kettle, stirring and heating the mixture to 90 ℃, adding 48.4g (the content is 99.95 percent and the excessive content is 5 percent) of toluene into a constant-pressure dropping funnel, starting to drop toluene, dropping the toluene for about 1 hour until the dropping process is finished, slowly raising the temperature to 105 ℃, keeping the temperature at 120 ℃ for reaction for 5 hours, keeping the reaction pressure at-0.008 MPa, sampling and detecting that the raw materials are completely reacted, cooling the temperature to 60 ℃, adding 20ml of water for hydrolysis, the hydrolysis temperature is 50 ℃, centrifuging the mixture to obtain a 4,4 '-dimethyldiphenylsulfone crude product and a centrifugal mother liquor (an iron trichloride aqueous solution), continuously cooling the temperature to below 40 ℃ after hydrolysis, adding 240 g of dichloromethane into the 4, 4' -dimethyldiphenylsulfone crude product, stirring and heating the temperature to 40 ℃, adding an ice brine bath, cooling the temperature to 10 ℃, precipitating crystals, performing suction filtration, precipitation, Drying to obtain 122.66 g of 4, 4' -dimethyl diphenyl sulfone, the detection content is 99.47%, and the experimental yield is 99.17%.
Example 5
Adding 95.8g (the content is 99.5 percent and 0.5 mol) of paratoluensulfonyl chloride and 4.5g of ferric trichloride into a 500ml four-product bottle, heating the mixture in an oil bath kettle, stirring and heating the mixture to 90 ℃, adding 48.4g (the content is 99.95 percent and the excessive content is 5 percent wt) of toluene into a constant-pressure dropping funnel, starting to drop toluene, dropping the toluene for about 1 hour until the dropping process is finished, slowly raising the temperature to 105 ℃, keeping the temperature at 128 ℃ for reaction for 2 hours, keeping the reaction pressure at-0.015 MPa, sampling and detecting that the raw materials are completely reacted, cooling the reaction product to 60 ℃, adding 20ml of water for hydrolysis, hydrolyzing the hydrolysis temperature at 90 ℃, centrifuging the reaction product to obtain a 4,4 '-dimethyl diphenyl sulfone crude product and a centrifugal mother liquor (an iron trichloride aqueous solution), continuously cooling the temperature to be below 40 ℃ after hydrolysis, adding 240 g of dichloromethane into the 4, 4' -dimethyl diphenyl sulfone crude product, stirring and heating the reaction product to 40 ℃, adding an ice brine bath, cooling the temperature to 8 ℃, precipitating crystals, filtering the crystals, precipitating, filtering, and filtering the crystals, Drying to obtain 122.48 g of 4, 4' -dimethyl diphenyl sulfone, the detection content is 99.44%, and the experimental yield is 98.99%.
Example 6
Adding 95.8g (content: 99.5%, 0.5 mol) of p-toluenesulfonyl chloride and 4.5g of ferric trichloride into a 500ml four-product bottle, heating in an oil bath kettle, stirring and heating to 90 ℃, adding 48.4g (toluene content: 99.95%, excessive 5 wt%) of toluene into a constant-pressure dropping funnel, starting to drop toluene, dropping for about 1 hour until the dropping process is finished, slowly raising the temperature to 120 ℃, keeping the temperature at 130 ℃ for reaction for 3 hours, keeping the reaction pressure at-0.01 MPa, sampling and detecting that the raw materials are completely reacted, cooling to 60 ℃, adding 20ml of water for hydrolysis, hydrolyzing at the hydrolysis temperature of 80 ℃, centrifuging to obtain a 4,4 '-dimethyldiphenylsulfone crude product and a centrifugal mother liquor (ferric trichloride aqueous solution), continuously cooling to below 40 ℃ after hydrolysis, adding 240 g of dichloromethane into the 4, 4' -dimethyldiphenylsulfone crude product, stirring and heating to 40 ℃, adding an ice brine bath, cooling to 10 ℃, precipitating crystals, filtering, and carrying out suction filtration, Drying to obtain 121.85 g of 4, 4' -dimethyl diphenyl sulfone, with the detection content of 99.43% and the experimental yield of 98.48%.
Example 7
Adding 95.8g (content: 99.5%, 0.5 mol) of p-toluenesulfonyl chloride and 4.5g of ferric trichloride into a 500ml four-product bottle, heating in an oil bath kettle, stirring and heating to 90 ℃, adding 48.4g (toluene content: 99.95%, excessive 5 wt%) of toluene into a constant-pressure dropping funnel, starting to drop toluene, dropping for about 1 hour until the dropping process is finished, slowly raising the temperature to 110 ℃, keeping the temperature at 120 ℃ for reaction for 4 hours, keeping the reaction pressure at-0.005 MPa, sampling and detecting that the raw materials are completely reacted, cooling to 60 ℃, adding 20ml of water for hydrolysis, hydrolyzing at the hydrolysis temperature of 30 ℃, centrifuging to obtain a 4,4 '-dimethyldiphenylsulfone crude product and a centrifugal mother liquor (ferric trichloride aqueous solution), continuously cooling to below 40 ℃ after hydrolysis, adding 240 g of dichloromethane into the 4, 4' -dimethyldiphenylsulfone crude product, stirring and heating to 40 ℃, adding an ice brine bath, cooling to 5 ℃, precipitating crystals, filtering, and separating out, Drying to obtain 121.94 g of 4, 4' -dimethyl diphenyl sulfone, the detection content is 99.06%, and the experimental yield is 98.18%.
The above-described embodiments of the present invention should not be construed as limiting the scope of the present invention. Any other corresponding changes and modifications made according to the technical idea of the present invention should be included in the protection scope of the claims of the present invention.
Claims (7)
1. A preparation method of 4, 4' -dimethyl diphenyl sulfone is characterized by comprising the following steps:
(1) condensation reaction; mixing paratoluensulfonyl chloride with ferric trichloride, heating, dripping toluene at 90-120 ℃, keeping the temperature at 120-130 ℃ after finishing dripping, and carrying out heat preservation reaction for 2-5 hours, wherein the reaction pressure is micro negative pressure;
(2) hydrolysis: after the condensation reaction is finished, hydrolyzing incompletely reacted p-toluenesulfonyl chloride at 20-90 ℃, cooling and centrifuging after the hydrolysis is finished to obtain a 4, 4' -dimethyl diphenyl sulfone crude product and a centrifugal mother solution;
(3) refining: and (3) dissolving the 4,4 '-dimethyl diphenyl sulfone crude product by adding a solvent, cooling, recrystallizing and filtering to obtain a 4, 4' -dimethyl diphenyl sulfone refined product.
2. The method for producing 4, 4' -dimethyldiphenyl sulfone according to claim 1, wherein in the step (1), the micro negative pressure is from-0.005 to-0.015 MPa.
3. The method according to claim 1, wherein the temperature of the mixture in step (2) is reduced to 40 ℃ or lower.
4. The method for producing 4, 4' -dimethyldiphenylsulfone as claimed in claim 1, wherein in the step (3), the solvent is dichloromethane, dichloroethane, methanol or ethanol.
5. The method for producing 4, 4' -dimethyldiphenyl sulfone according to claim 4, wherein the solvent is methylene chloride.
6. The process according to claim 4, wherein the temperature is raised to 40 ℃ in the step (3) when the solvent is added for dissolution.
7. The method for preparing 4, 4' -dimethyldiphenylsulfone as claimed in claim 6, wherein in the step (3), the temperature is reduced to 5-10 ℃.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1249737A (en) * | 1997-03-12 | 2000-04-05 | 罗狄亚化学公司 | Method for acylation or sulphonation of aromatic compound |
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- 2021-12-08 CN CN202111493217.7A patent/CN113880736A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1249737A (en) * | 1997-03-12 | 2000-04-05 | 罗狄亚化学公司 | Method for acylation or sulphonation of aromatic compound |
Non-Patent Citations (3)
| Title |
|---|
| JULIEN MARQUIE 等: "Acylation and Related Reactions under Microwaves. 4.Sulfonylation Reactions of Aromatics", 《J. ORG. CHEM.》 * |
| M. V. ALEXANDER 等: "Sulfonylation reactions of aromatics using FeCl3-based ionic liquids", 《JOURNAL OF MOLECULAR CATALYSIS A： CHEMICAL》 * |
| RAVI P. SINGH 等: "An ef®cient method for aromatic Friedel-Crafts alkylation, acylation, benzoylation, and sulfonylation reactions", 《TETRAHEDRON》 * |
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