CN100497305C - Method for preparing ethylsulfonyl acetonitrile - Google Patents
Method for preparing ethylsulfonyl acetonitrile Download PDFInfo
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- CN100497305C CN100497305C CNB2007100355121A CN200710035512A CN100497305C CN 100497305 C CN100497305 C CN 100497305C CN B2007100355121 A CNB2007100355121 A CN B2007100355121A CN 200710035512 A CN200710035512 A CN 200710035512A CN 100497305 C CN100497305 C CN 100497305C
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- acetonitrile
- ethylsulfonyl
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- hydrogen peroxide
- acetic acid
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Abstract
Preparation of ethylsulfonyl-methyl cyanide is carried out by: taking acetic acid as reactive solvent, taking hydrogen peroxide as oxidant and oxidizing ethyl phenyl methyl cyanide into ethylsulfonyl-methyl cyanide. It's convenient, controllable and efficient. It has gentle reactive condition, higher content and can be used for industrial production. It can be used to produce super-efficient sulfonylurea herbicide jade pyrsulfogentian intermediate.
Description
Technical field
The present invention relates to the preparation method of ethylsulfonyl acetonitrile.
Background technology
Ethylsulfonyl acetonitrile is the intermediate (patent US4774337) of preparation ultra-high efficiency sulfonylurea herbicide rimsulfuron 25.Ethylsulfonyl acetonitrile is to make by thio-ether type compounds ethylmercapto group acetonitrile is oxidized to sulfone according to the literature, and this method mainly contains following several:
1.. make solvent with methylene dichloride, metachloroperbenzoic acid is made oxygenant (WO Patent 2004101505).
2.. make solvent with acetic acid, hydrated sodium perborate do oxygenant (Nie Hui, Tong Xiaoxu, military quoted passage. Hebei chemical industry .1996,4:38～45.Zhou Weiqing, Zhang Likang, Xu Xiaoqing is just opening. Chinese Journal of Inorganic Chemistry .1992,1 (8): 88～90.Yue Guoren, Wang Jianhua is just being opened. applied chemistry .1995,12 (4): 93～95. etc.).
3.. make solvent with acetic acid, hydrogen peroxide as oxidant (WO Patent 2004101505; Zhao Liqin opens great waves. chemistry world .2000,9:500～501.).
In existing these methods, the costing an arm and a leg of the 1. used oxygenant metachloroperbenzoic acid of method.Method 2. in, hydrated sodium perborate is reduced the back and produces a large amount of inorganic salt, aftertreatment difficulty.Method 3. in, the amount ratio of hydrogen peroxide and acetic acid is bigger, hydrogen peroxide generally needs excessive 2～3 times of amounts, the consumption of acetic acid is 30～40 times of reactant, causes material cost too high, reduces the consumption of hydrogen peroxide, then reaction not exclusively, if reduce the consumption of acetic acid, can unavoidably occur in the reaction process acutely towards warm phenomenon, even might be explosion caused; Because hydrogen peroxide is excessive more, before slide recovery aqueous acetic acid is steamed in decompression, must destroys excessive hydrogen peroxide, otherwise explosion caused possibility is arranged with reductive agent.
Summary of the invention
The present invention is to provide with the ethylmercapto group acetonitrile is raw material, is reaction solvent with acetic acid, and hydrogen peroxide is an oxygenant, and compounds such as tungstic acid hydrate sodium, ammonium molybdate or benzene selenic acid are the method for the synthetic ethylsulfonyl acetonitrile of catalyzer, and its chemical equation is:
Specific embodiment of the present invention is that 1 normal ethylmercapto group acetonitrile is mixed with 0.5～1.5 normal acetic acid, add 0.01～0.03 normal catalyzer, drip 2～4 normal hydrogen peroxide under the room temperature, temperature of reaction is controlled at 40 ℃～80 ℃, reaction times 1h～5h.Reaction finishes, and behind 50 ℃～90 ℃ a certain amount of aqueous acetic acids of reclaim under reduced pressure of temperature control, adds an amount of water and makes the salt dissolving.Divide oil-yielding stratum, water layer is with a kind of extraction the in organic solvent chloroform, the ethyl acetate, merging organic layer, decompression and solvent recovery get final product the product ethylsulfonyl acetonitrile.Yield is more than 90%, and content is more than 98%.
The present invention compares with present existent method, have reaction temperature and, simple to operate, product yield, content height greatly reduce the advantages such as consumption of acetic acid and hydrogen peroxide.Because the consumption of hydrogen peroxide almost can drop to the Theoretical Calculation equivalent, so aftertreatment need not to destroy excessive hydrogen peroxide, and directly the reclaim under reduced pressure aqueous acetic acid gets final product.Be particularly suitable for suitability for industrialized production.
Embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment 1
In the three-necked bottle of the 3000mL that has thermometer, prolong, constant pressure funnel, agitator, add the ethylmercapto group acetonitrile of 375.0g (3.71mol), acetic acid and the 18.0g Disodium tungstate (Na2WO4) dihydrate of 225.0g (3.75mol), drip 984.0g (7.8mol) hydrogen peroxide (content 27.0%) under the room temperature, 40 ℃～50 ℃ following stirring reactions 2 hours, decompression steamed about 750.0g aqueous acetic acid then.Cooling adds an amount of water and makes the salt dissolving.Divide oil-yielding stratum, water layer 500mL chloroform extraction 2 times.Merge organic layer, the reclaim under reduced pressure chloroform gets product 461.9g, thick yield 93.6%, content 98.4% (chromatogram ration analysis).
1H?NMR(CDCl
3)δ：(ppm)1.50～1.55(t，3H，-CH
2C
H 3 )，3.30～3.37(q，2H，-CH
2-)，3.97～3.98(m，2H，-CH
2CN).
Embodiment 2
In the three-necked bottle of the 3000mL that has thermometer, prolong, constant pressure funnel, agitator, add the ethylmercapto group acetonitrile of 375.0g (3.71mol), acetic acid and the 18.0g Disodium tungstate (Na2WO4) dihydrate of 225.0g (3.75mol), drip 984.0g (7.8mol) hydrogen peroxide (content 27.0%) under the room temperature, 40 ℃～50 ℃ following stirring reactions 2 hours, decompression steamed about 750.0g aqueous acetic acid then.Cooling adds an amount of water and makes the salt dissolving.Divide oil-yielding stratum, water layer 500mL ethyl acetate extraction 2 times.Merge organic layer, the reclaim under reduced pressure ethyl acetate gets product 470.0g, thick yield 95.2%, content 98.6% (chromatogram ration analysis).
Claims (5)
1, a kind of preparation method of ethylsulfonyl acetonitrile is characterized in that with the ethylmercapto group acetonitrile be raw material, is reaction solvent with acetic acid, is oxygenant with the hydrogen peroxide, is catalyzer with tungstic acid hydrate sodium, synthetic ethylsulfonyl acetonitrile, and its chemical equation is:
Concrete steps are that the ethylmercapto group acetonitrile is mixed with acetic acid; add catalyzer; drip hydrogen peroxide under the room temperature; temperature of reaction is controlled at 40 ℃～80 ℃, and reaction finishes, behind 50 ℃～90 ℃ reclaim under reduced pressure aqueous acetic acids of temperature control; divide oil-yielding stratum; the water layer organic solvent extraction merges organic layer, and decompression and solvent recovery promptly gets ethylsulfonyl acetonitrile.
2, the preparation method of ethylsulfonyl acetonitrile according to claim 1, the equivalence ratio that it is characterized in that catalyzer and ethylmercapto group acetonitrile is 0.01: 1～0.03: 1.
3, the preparation method of ethylsulfonyl acetonitrile according to claim 1, the equivalence ratio that it is characterized in that ethylmercapto group acetonitrile and acetic acid is 1: 0.5～1: 1.5.
4, the preparation method of ethylsulfonyl acetonitrile according to claim 1, the equivalence ratio that it is characterized in that ethylmercapto group acetonitrile and hydrogen peroxide is 1: 2～1: 4.
5, the preparation method of ethylsulfonyl acetonitrile according to claim 1, the organic solvent that it is characterized in that extracting usefulness is a kind of in chloroform, the ethyl acetate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100355121A CN100497305C (en) | 2007-08-06 | 2007-08-06 | Method for preparing ethylsulfonyl acetonitrile |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100355121A CN100497305C (en) | 2007-08-06 | 2007-08-06 | Method for preparing ethylsulfonyl acetonitrile |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101100450A CN101100450A (en) | 2008-01-09 |
| CN100497305C true CN100497305C (en) | 2009-06-10 |
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| CNB2007100355121A Expired - Fee Related CN100497305C (en) | 2007-08-06 | 2007-08-06 | Method for preparing ethylsulfonyl acetonitrile |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102216264B (en) | 2008-11-17 | 2014-01-15 | 住友精化株式会社 | Sulfone compound |
| KR20120025588A (en) * | 2009-06-09 | 2012-03-15 | 스미또모 세이까 가부시키가이샤 | Process for preparation of alkyl sulfone compounds |
| CN102086167B (en) * | 2010-12-09 | 2013-05-08 | 济南大学 | Method for preparing ethylsulfonyl acetonitrile |
| CN102351757A (en) * | 2011-08-25 | 2012-02-15 | 吴江市北厍盛源纺织品助剂厂 | Method for preparing 4.4-dichlorodiphenyl sulfone by using sulfoxide oxidation |
| CN102827043A (en) * | 2012-09-21 | 2012-12-19 | 中国乐凯胶片集团公司 | Preparation method of 1,2-divinylsulfacetamidoethane |
| CN105461600B (en) * | 2015-12-18 | 2018-03-16 | 三门峡奥科化工有限公司 | A kind of preparation method of Methylethyl sulfone |
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2007
- 2007-08-06 CN CNB2007100355121A patent/CN100497305C/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| 由硫醚或亚砜氧化制砜的研究进展. 谭晓军等.化学研究，第15卷第3期. 2004 |
| 由硫醚或亚砜氧化制砜的研究进展. 谭晓军等.化学研究，第15卷第3期. 2004 * |
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| CN101100450A (en) | 2008-01-09 |
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Assignee: HUBEI CHISHUN CHEMICAL INDUSTRY Co.,Ltd. Assignor: HUNAN Research Institute OF CHEMICAL INDUSTRY Contract record no.: 2011420000242 Denomination of invention: Method for preparing ethylsulfonyl acetonitrile Granted publication date: 20090610 License type: Exclusive License Open date: 20080109 Record date: 20110916 |
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