CN110028429A - A kind of preparation method of paratoluensulfonyl chloride - Google Patents
A kind of preparation method of paratoluensulfonyl chloride Download PDFInfo
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- CN110028429A CN110028429A CN201910454956.1A CN201910454956A CN110028429A CN 110028429 A CN110028429 A CN 110028429A CN 201910454956 A CN201910454956 A CN 201910454956A CN 110028429 A CN110028429 A CN 110028429A
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- tosilate
- chloride
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- paratoluensulfonyl chloride
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- 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
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- 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
- C07C303/22—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 from sulfonic acids, by reactions not involving the formation of sulfo or halosulfonyl groups; from sulfonic halides by reactions not involving the formation of halosulfonyl groups
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind of preparation method of paratoluensulfonyl chloride, the method are as follows: tosilate, benzamide type catalyst, thionyl chloride, solvent are mixed, 60~80 DEG C of reaction 8~10h are warming up to, it is post-treated later, obtain product paratoluensulfonyl chloride；The method of the present invention uses benzamide type catalyst, with very high catalytic performance, carry out reaction can lower than thionyl chloride boiling point, therefore the dosage of thionyl chloride is reduced, and it realizes and at room temperature directly mixes material, reheat the mode of operation reacted, improve the safety of operation, the problem of greatly reducing in reporting style loss of material caused by excess thionyl chloride overflows in reaction process at high temperature and environmental hazard, it is at low cost, environmental-friendly, there is good prospects for commercial application.
Description
(1) technical field
The present invention relates to a kind of new methods of the tosilate recycled in waste water production paratoluensulfonyl chloride, and belonging to has
Machine synthesis technical field.
(2) background technique
Paratoluensulfonyl chloride is widely used in dyestuff, medicine, in pesticide industry as a kind of fine chemical product.?
In industrial production, a Main By product of paratoluensulfonyl chloride is paratoluenesulfonic acid sodium salt, there is very big COD in industrial wastewater
It is worth and is unable to direct emission.Waste water is carried out after being evaporated extraction, the crude salt of available paratoluenesulfonic acid sodium salt.This technique is mainly
Paratoluensulfonyl chloride is synthesized for crude salt, on the one hand forming material can be recycled, relevant item production cost has been saved,
On the other hand waste discharge amount is substantially reduced, mitigates the pressure of environmental protection of enterprise and three-protection design.
Currently, the common synthetic method about paratoluensulfonyl chloride is mainly tosylation method and tosilate chlorine
Change method.Wherein, tosilate chloridising reported at present, main sulfonate have paratoluenesulfonic acid sodium salt, to toluene sulphur
Sour potassium, paratoluenesulfonic acid ammonium salt and p-methyl benzenesulfonic acid magnesium etc..In general, the chlorination of these sulfonate is required using a large amount of dichloro
Sulfoxide had not only been used as chlorination reagent but also had been used as solvent.CN 102295587A reports a kind of chlorination using recycling paratoluenesulfonic acid sodium salt
Technique uses pyridine as catalyst, and reaction needs to carry out at 110 DEG C, greatly exceeds 80 DEG C of boiling point of thionyl chloride, because
This needs to be added dropwise thionyl chloride under liquid level, and safety difference and thionyl chloride, which are easy to overflow, causes loss of material and environment to endanger
Evil.The CN 107344922A report p-methyl benzenesulfonic acid magnesium poor using activity, under the protective condition of inert gas, with N, N-
Dimethylformamide is as solvent, and thionyl chloride reacts to obtain paratoluensulfonyl chloride as chlorination reagent, still, due to using
A large amount of n,N-Dimethylformamide needs to generate a large amount of spent acidic using a large amount of water washing as solvent in post-processing
Water, environmental protection pressure is big, also sufficiently expensive in price since solvent cannot recycle, and is unfavorable for industrial application.
(3) summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of preparation method of paratoluensulfonyl chloride, this method is used
The paratoluenesulfonic acid sodium salt or p-methyl benzenesulfonic acid magnesium extracted in industrial wastewater is primary raw material, prepares tolysulfonyl through chlorination reaction
Chlorine, yield reach 95% or more.
Technical scheme is as follows:
A kind of preparation method of paratoluensulfonyl chloride, the method are as follows:
By tosilate, benzamide type catalyst, thionyl chloride, solvent mix, be warming up to 60~80 DEG C reaction 8~
10h, it is post-treated later, obtain product paratoluensulfonyl chloride；
The tosilate, benzamide type catalyst, thionyl chloride mass ratio be 1:0.005~0.02:0.6~
0.7；
The volumetric usage of the solvent is calculated as 2~8mL/g with the quality of tosilate；
The benzamide type catalyst is N,N-dimethylformamide, N, in N- diethylformamide, N-METHYLFORMAMIDE
One or more kinds of arbitrary proportions mixture；
The solvent is selected from the mixing of one or more of toluene, dichloroethanes, acetonitrile, dimethylbenzene arbitrary proportion
Solvent；
The method of the post-processing are as follows: after reaction, reaction solution evaporating solvent under reduced pressure obtains crude product, is recrystallized, is obtained
To product paratoluensulfonyl chloride；Solvent used in the recrystallization is n-hexane, hexamethylene, methylene chloride, one in petroleum ether
The mixed solvent of kind or two or more arbitrary proportions；Also, being evaporated under reduced pressure solvent used in recovered solvent, recrystallization can not
It is directly applied through processing.
In the present invention, the tosilate be paratoluenesulfonic acid sodium salt or p-methyl benzenesulfonic acid magnesium, it is particularly, described to first
Benzene sulfonate can be obtained by industrial wastewater tosilate extraction with aqueous solution；
The industrial wastewater p-methyl benzenesulfonic acid saline solution comes from following technical process:
In the production process of 2 thiophene ethyl amine, intermediate 2 thiophene ethyl amine tosilate inorganic base is free to obtain 2-
Thiophene ethamine, 2 thiophene ethyl amine is extracted with organic solvent (such as toluene) in last handling process, and the waste water of generation is to toluene
Sulfonic acid saline solution；
By the method for industrial wastewater tosilate extraction with aqueous solution tosilate are as follows:
It is layered after first being extracted with organic solvent (such as toluene) after p-methyl benzenesulfonic acid saline solution heating (50~90 DEG C),
Organic layer applies 2 thiophene ethyl amine production, decrease temperature crystalline after water layer concentration, and filtration drying obtains tosilate.
The beneficial effects of the present invention are:
Compared to reported mode, the method for the present invention uses Carbox amide as catalyst, and catalytic activity is high,
It carry out reaction can at a temperature of 60~80 DEG C are relatively low, while the dosage of thionyl chloride is reduced to 1.1 molar equivalents,
Effectively prevent environmental pollution brought by the spilling of thionyl chloride；Solvent using recyclable solvent, after enabling reaction
It recycles, greatly reduces industrial cost；Post-processing recycled by the way of directly recrystallizing, effectively prevents generating
The pollution such as waste water, exhaust gas, has good industrial prospect.
Since the preparation method of the paratoluensulfonyl chloride is had very high catalytic performance, is made using benzamide type catalyst
Reaction can be carried out in the case where being lower than thionyl chloride boiling point, therefore reduce the dosage of thionyl chloride, and realize room
Directly material is mixed under temperature, the mode of operation reacted is reheated, improves the safety of operation, greatly reduce
The problem of loss of material caused by excess thionyl chloride overflows in reaction process at high temperature in reporting style and environmental hazard.
(4) specific embodiment
Below by specific embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited in
This.
Embodiment 1:
At room temperature, at 100 grams of crude salt of the middle addition paratoluenesulfonic acid sodium salt of round-bottomed flask (500mL), 200 milliliters of toluene, N,
It 1 milliliter and 67 grams of thionyl chloride of dinethylformamide, is mixed after five minutes, it, will after being warming up to 65 DEG C of 8 hours of reaction
Reaction is changed to vacuum distillation apparatus, and toluene is steamed from reaction solution, is cooled to room temperature after being evaporated, and is added 40 milliliters of hexamethylene, adds
Hot cooled and filtered obtains 93 grams of product, yield 95%.
Embodiment 2:
At room temperature, 100 grams of crude salt of paratoluenesulfonic acid sodium salt are added in round-bottomed flask (500mL), 200 milli of dichloroethanes
It rises, 1.1 milliliters and 67 grams of thionyl chloride of n,N-dimethylacetamide, is mixed after five minutes, it is 8 small to be warming up to 65 DEG C of reactions
Reaction is changed to vacuum distillation apparatus, dichloroethanes is steamed from reaction solution by Shi Hou, is cooled to room temperature after being evaporated, and petroleum is added
40 milliliters of ether, heating cooled and filtered obtains 93 grams of product, yield 95%.
Embodiment 3:
At room temperature, at 100 grams of crude salt of the middle addition p-methyl benzenesulfonic acid magnesium of round-bottomed flask (500mL), 200 milliliters of toluene, N,
It 1 milliliter and 70 grams of thionyl chloride of dinethylformamide, is mixed after five minutes, it, will after being warming up to 65 DEG C of 10 hours of reaction
Reaction is changed to vacuum distillation apparatus, and dichloroethanes is steamed from reaction solution, is cooled to room temperature after being evaporated, and 40 milli of n-hexane is added
It rises, heating cooled and filtered obtains 95 grams of product, yield 98%.
Claims (7)
1. a kind of preparation method of paratoluensulfonyl chloride, which is characterized in that the method are as follows:
Tosilate, benzamide type catalyst, thionyl chloride, solvent are mixed, 60~80 DEG C of 8~10h of reaction are warming up to,
It is post-treated later, obtain product paratoluensulfonyl chloride；
The tosilate, benzamide type catalyst, thionyl chloride mass ratio be 1:0.005~0.02:0.6~0.7；
The benzamide type catalyst is N,N-dimethylformamide, N, one in N- diethylformamide, N-METHYLFORMAMIDE
The mixture of kind or two or more arbitrary proportions.
2. the preparation method of paratoluensulfonyl chloride as described in claim 1, which is characterized in that the solvent is selected from toluene, two
The mixed solvent of one or more of chloroethanes, acetonitrile, dimethylbenzene arbitrary proportion.
3. the preparation method of paratoluensulfonyl chloride as described in claim 1, which is characterized in that the volumetric usage of the solvent with
The quality of tosilate is calculated as 2~8mL/g.
4. the preparation method of paratoluensulfonyl chloride as described in claim 1, which is characterized in that the method for the post-processing are as follows:
After reaction, reaction solution evaporating solvent under reduced pressure obtains crude product, is recrystallized, and product paratoluensulfonyl chloride is obtained；The heavy knot
Solvent used in crystalline substance is that the mixing of one or more of n-hexane, hexamethylene, methylene chloride, petroleum ether arbitrary proportion is molten
Agent.
5. the preparation method of paratoluensulfonyl chloride as described in claim 1, which is characterized in that the tosilate is pair
Toluenesulfonic acid sodium salt or p-methyl benzenesulfonic acid magnesium.
6. the preparation method of paratoluensulfonyl chloride as described in claim 1, which is characterized in that the tosilate is by work
Industry waste water tosilate extraction with aqueous solution obtains.
7. the preparation method of paratoluensulfonyl chloride as claimed in claim 6, which is characterized in that the industrial wastewater is to toluene sulphur
Acid salt aqueous solution comes from following technical process: in the production process of 2 thiophene ethyl amine, intermediate 2 thiophene ethyl amine p-methyl benzenesulfonic acid
Salt inorganic base is free to obtain 2 thiophene ethyl amine, and 2 thiophene ethyl amine is extracted with organic solvent in last handling process, the waste water of generation
As p-methyl benzenesulfonic acid saline solution；
By the method for industrial wastewater tosilate extraction with aqueous solution tosilate are as follows: by p-methyl benzenesulfonic acid saline solution
It is layered after first being extracted with organic solvent after heating, organic layer applies 2 thiophene ethyl amine production, decrease temperature crystalline after water layer concentration, filtering
It is dried to obtain tosilate.
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| CN201910454956.1A CN110028429A (en) | 2019-05-29 | 2019-05-29 | A kind of preparation method of paratoluensulfonyl chloride |
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| CN201910454956.1A CN110028429A (en) | 2019-05-29 | 2019-05-29 | A kind of preparation method of paratoluensulfonyl chloride |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111040165A (en) * | 2019-12-26 | 2020-04-21 | 白银图微新材料科技有限公司 | Polysulfonate polymer and polymerization method thereof |
| CN114105828A (en) * | 2021-12-17 | 2022-03-01 | 济南立德医药技术有限公司 | Synthetic method of p-toluenesulfonyl chloride |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03232859A (en) * | 1990-02-09 | 1991-10-16 | Ube Ind Ltd | Pyrazole derivative, its production and germicide |
| CN102295587A (en) * | 2011-05-26 | 2011-12-28 | 安徽丰乐农化有限责任公司 | New preparation technology of p-toluenesulfonyl chloride |
| CN103351376A (en) * | 2013-07-02 | 2013-10-16 | 浙江燎原药业有限公司 | Synthetic method of 2-thiophene ethylamine |
-
2019
- 2019-05-29 CN CN201910454956.1A patent/CN110028429A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03232859A (en) * | 1990-02-09 | 1991-10-16 | Ube Ind Ltd | Pyrazole derivative, its production and germicide |
| CN102295587A (en) * | 2011-05-26 | 2011-12-28 | 安徽丰乐农化有限责任公司 | New preparation technology of p-toluenesulfonyl chloride |
| CN103351376A (en) * | 2013-07-02 | 2013-10-16 | 浙江燎原药业有限公司 | Synthetic method of 2-thiophene ethylamine |
Non-Patent Citations (1)
| Title |
|---|
| 王俊等: "精喹禾灵废水中对甲苯磺酰氯的回收", 《现代农药》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111040165A (en) * | 2019-12-26 | 2020-04-21 | 白银图微新材料科技有限公司 | Polysulfonate polymer and polymerization method thereof |
| CN114105828A (en) * | 2021-12-17 | 2022-03-01 | 济南立德医药技术有限公司 | Synthetic method of p-toluenesulfonyl chloride |
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