CN101906073A - Method for synthesizing and purifying fipronil - Google Patents
Method for synthesizing and purifying fipronil Download PDFInfo
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- CN101906073A CN101906073A CN2009100328208A CN200910032820A CN101906073A CN 101906073 A CN101906073 A CN 101906073A CN 2009100328208 A CN2009100328208 A CN 2009100328208A CN 200910032820 A CN200910032820 A CN 200910032820A CN 101906073 A CN101906073 A CN 101906073A
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- worm nitrile
- fluorine worm
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- purification
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Abstract
The invention relates to a preparation method of an efficient insecticide-fipronil, in particular to a method for synthesizing and purifying fipronil, in which CF3SO2Na and 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoro-methylphenyl)pyrazol are adopted. The method is characterized in that CF3SO2Na reacts with an appropriate reaction reagent and then fully reacts with 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethyl phenyl)pyrazol to obtain a coarse product of the compound 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethyl phenyl)-4-trifluoromethyl sulfinyl pyrazol and then the coarse product is purified to obtain fipronil with content of 97.5%. The whole method is easy in raw material acquisition, simple and convenient in process conditions and excellent in product quality.
Description
Technical field
That the present invention relates to is the preparation method of efficient pesticides fluorine worm nitrile, is specially to adopt CF
3SO
2Synthetic and the purification fluorine worm nitrile method of Cl and 5-amino-3-cyano group-1-(2,6-dichlor-4-trifluoromethyl phenyl) pyrazoles.
Background technology
Fluorine worm nitrile is the efficient pesticides of at first being developed by French Luo Na-Rhone-Poulenc; chemical name: 5-amino-3-cyano group-1-(2; 6-dichlor-4-trifluoromethyl phenyl)-the 4-trifluoromethyl sulfinyl pyrazole; the chloride channel that fluorine worm nitrile is regulated by γ-An Jidingsuan disturbs the passage of chlorion, destroys the active of normal central nervous system and cause individual death under the situation of q.s.Because the effect of this uniqueness makes fluorine worm nitrile have the distinguishing feature that is different from common insecticides.Preparation fluorine worm nitrile method mainly contains three kinds of routes at present: route 1 is by 5-amino-3-cyano group-1-(2,6-dichlor-4-trifluoromethyl phenyl) pyrazoles and trifluoromethylthio haloalkane reaction, introduce trifluoromethylthio, obtain 5-amino-3-cyano group-1-(2 through the metachloroperbenzoic acid oxidation again, 6-dichlor-4-trifluoromethyl phenyl)-the 4-trifluoromethyl sulfinyl pyrazole, deficiency is that trifluoromethylthio haloalkane toxicity is high, and operating process is difficulty; Route 2 is by 5-amino-3-cyano group-1-(2,6-dichlor-4-trifluoromethyl phenyl) the two sulfo-things of pyrazoles preparation earlier, obtain 5-amino-3-cyano group-1-(2 with haloalkane through trifluoroacetic acid/hydrogen peroxide oxidation, 6-dichlor-4-trifluoromethyl phenyl)-and the 4-trifluoromethyl sulfinyl pyrazole, deficiency is that production cost is too high; Route 3 is by 5-amino-3-cyano group-1-(2; 6-dichlor-4-trifluoromethyl phenyl) pyrazoles and sulfinyl substituent reaction one-step synthesis obtains 5-amino-3-cyano group-1-(2; 6-dichlor-4-trifluoromethyl phenyl)-and the 4-trifluoromethyl sulfinyl pyrazole, deficiency is that yield is not high.
Summary of the invention
Purpose of the present invention adopts CF
3SO
2Synthetic and the purification fluorine worm nitrile method of Cl and 5-amino-3-cyano group-1-(2,6-dichlor-4-trifluoromethyl phenyl) pyrazoles, thus overcome the deficiency that existing technology of preparing exists.
Technical solution of the present invention is: with CF
3SO
2Cl and suitable reactions reagent react; fully react with 5-amino-3-cyano group-1-(2,6-dichlor-4-trifluoromethyl phenyl) pyrazoles again, obtain compound 5-amino-3-cyano group-1-(2; 6-dichlor-4-trifluoromethyl phenyl)-and 4-trifluoromethyl sulfinyl pyrazole crude product, reaction formula is:
Synthetic and method of purification comprises step: earlier with CF
3SO
2Cl joins in the suitable reactions reagent, temperature is controlled to be 0-5 ℃, reaction is overflowed until no gas, be warming up to 15-20 ℃ and be incubated 8 hours, add 5-amino-3-cyano group-1-(2,6-dichlor-4-trifluoromethyl phenyl) pyrazoles and right-toluenesulphonic acids dimethylamine salt mixture then, add catalyzer simultaneously, the pressure reducing and steaming solvent obtains the former medicine of fluorine worm nitrile; The former medicine of fluorine worm nitrile adds water washing, filtration, and filter cake gets the faint yellow solid thing with washed with dichloromethane, drying; The mixture that adds N-BUTYL ACETATE and dichloroethyl ether again stirs and heats up, fully dissolving, filtration, and xln is separated out in cooling then, and crystal obtains the fluorine worm nitrile of content 97.5% through suction filtration.
In the above-mentioned steps, suitable reactions reagent is sulfur oxychloride and dry-out benzene liquid mixed solution, cools off and maintains the temperature at 0 ℃;
In the above-mentioned steps, controlled temperature is 15 ℃, stirs 0.5 hour, is warming up to 35-45 ℃ of reaction 12 hours then;
In the above-mentioned steps, N-BUTYL ACETATE and dichloroethyl ether are made into the mixture of 1: 1 ratio;
The present invention has found suitable reaction reagent and reaction conditions, and the reagent raw material is easy to get and easily preparation, and condition is easy, the reactive behavior height, and flow process is short, comprehensive yield height; And the preparation method who has found suitable solvent carries out compound and purifies, and solved the purification problem of high-content 5-amino-3-cyano group-1-(2,6-dichlor-4-trifluoromethyl phenyl)-4-trifluoromethyl sulfinyl pyrazole product; Whole synthetic and raw material that method of purification adopts is easy to get, and processing condition are easy, and the product product are of fine quality.
Embodiment
The present invention is described in detail below in conjunction with specific embodiment
Embodiment
At a four-hole boiling flask that has electric mixer, thermometer, reflux condensing tube, and flask places the container that can put frozen water, drop into earlier 29.0 gram (0.22 mole) sulfur oxychloride and 250ml dry-out benzene liquid, cool off and maintain the temperature at 0 ℃, divides and drop into 45.0 for 3 times altogether and restrain (0.5 mole) CF
3SO
2Cl, temperature of reaction is controlled to be 0-5 ℃, and reaction is overflowed until no gas, is warming up to 15-20 ℃ and be incubated 8 hours; Add 50.0 gram (0.16 mole) 5-amino-3-cyano group-1-(2 then, 6-dichlor-4-trifluoromethyl phenyl) pyrazoles and 52.8 the gram (0.17 mole) right-toluenesulphonic acids dimethylamine salt mixture, add 1 gram catalyzer simultaneously, controlled temperature is 15 ℃, stirred 0.5 hour, be warming up to 35-45 ℃ of reaction 12 hours then, the pressure reducing and steaming solvent obtains solid reactant; The gained solids adds water washing, filtration, and filter cake gets faint yellow solid thing 61.2 grams with washed with dichloromethane, drying; This faint yellow solid thing adds the mixture that 125 gram N-BUTYL ACETATEs and 125 restrain dichloroethyl ether, and stir and heat up, fully dissolving, filtration, xln is separated out in cooling then, and crystal obtains the white solid thing through suction filtration.Gained white solid thing is through being accredited as 5-amino-3-cyano group-1-(2,6-dichlor-4-trifluoromethyl phenyl)-4-trifluoromethyl sulfinyl pyrazole, and product weighs 56.5 grams, measures through HPLC, and its content is 97.5%, and ultimate yield is 78%.After measured, fusing point is 202.5 ℃.
Claims (4)
1. the synthetic and method of purification of fluorine worm nitrile is characterized in that: with CF
3SO
2Cl and suitable reactions reagent react; fully react with 5-amino-3-cyano group-1-(2,6-dichlor-4-trifluoromethyl phenyl) pyrazoles again, obtain compound 5-amino-3-cyano group-1-(2; 6-dichlor-4-trifluoromethyl phenyl)-and 4-trifluoromethyl sulfinyl pyrazole crude product, reaction formula is:
Synthetic and method of purification comprises step: earlier with CF
3SO
2Cl joins in the suitable reactions reagent, temperature is controlled to be 0-5 ℃, reaction is overflowed until no gas, be warming up to 15-20 ℃ and be incubated 8 hours, add 5-amino-3-cyano group-1-(2,6-dichlor-4-trifluoromethyl phenyl) pyrazoles and tosic acid dimethylamine salt mixture then, add catalyzer simultaneously, the pressure reducing and steaming solvent obtains the former medicine of fluorine worm nitrile; The former medicine of fluorine worm nitrile adds water washing, filtration, and filter cake gets the faint yellow solid thing with washed with dichloromethane, drying; The mixture that adds N-BUTYL ACETATE and dichloroethyl ether again stirs and heats up, fully dissolving, filtration, and xln is separated out in cooling then, and crystal obtains the fluorine worm nitrile of content 97.5% through suction filtration.
2. the synthetic and method of purification of fluorine worm nitrile according to claim 1, it is characterized in that: suitable reactions reagent is sulfur oxychloride and dry-out benzene liquid mixed solution, cools off and maintains the temperature at 0 ℃.
3. the synthetic and method of purification of fluorine worm nitrile according to claim 1, it is characterized in that: controlled temperature is 15 ℃, stirs 0.5 hour, is warming up to 35-45 ℃ of reaction 12 hours then.
4. the synthetic and method of purification of fluorine worm nitrile according to claim 1, it is characterized in that: N-BUTYL ACETATE and dichloroethyl ether are made into the mixture of 1: 1 ratio.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100328208A CN101906073A (en) | 2009-06-03 | 2009-06-03 | Method for synthesizing and purifying fipronil |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100328208A CN101906073A (en) | 2009-06-03 | 2009-06-03 | Method for synthesizing and purifying fipronil |
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| CN101906073A true CN101906073A (en) | 2010-12-08 |
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| CN2009100328208A Pending CN101906073A (en) | 2009-06-03 | 2009-06-03 | Method for synthesizing and purifying fipronil |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102093295A (en) * | 2011-03-10 | 2011-06-15 | 江苏长青农化股份有限公司 | Synthesis method of insecticide Fipronil |
| WO2012095871A3 (en) * | 2011-01-14 | 2012-10-04 | Keki Hormusji Gharda | Polymorphism in 5-amino- 1 -(2,6-dichloro-4- trifluoromethylphenyl)-3-cyano-4-trifluoro methyl sulfinyl pyrazole |
| CN103547572A (en) * | 2011-05-30 | 2014-01-29 | K·H·伽达 | Process for synthesis of fipronil |
| GB2516446A (en) * | 2013-07-22 | 2015-01-28 | Rotam Agrochem Int Co Ltd | Process for the preparation of n-substituted pyrazole compounds and products of the same |
| CN104557713A (en) * | 2013-10-22 | 2015-04-29 | 江苏托球农化有限公司 | Preparation method of high-purity fipronil |
| CN104926729A (en) * | 2014-03-18 | 2015-09-23 | 上海泰禾化工有限公司 | Method for synthesis of high-purity fipronil |
| CN106699615A (en) * | 2016-12-28 | 2017-05-24 | 江苏托球农化股份有限公司 | Preparation process of trifluoromethyl sulfinyl chloride |
| CN113825743A (en) * | 2019-03-19 | 2021-12-21 | 格哈达化工有限公司 | Method for synthesizing fipronil |
| CN115353490A (en) * | 2022-09-26 | 2022-11-18 | 安徽美诺华药物化学有限公司 | Purification process of fipronil |
| CN115594635A (en) * | 2022-09-29 | 2023-01-13 | 浙江美诺华药物化学有限公司（Cn） | Synthetic method of dechlorinated fipronil |
| CN115650919A (en) * | 2022-04-13 | 2023-01-31 | 华东理工大学 | Method for preparing fipronil from trichloromethyl sulfinyl chloride |
-
2009
- 2009-06-03 CN CN2009100328208A patent/CN101906073A/en active Pending
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9198421B2 (en) | 2011-01-14 | 2015-12-01 | Keki Hormusji Gharda | Polymorphism in 5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-4-trifluoro methyl sulfinyl pyrazole |
| WO2012095871A3 (en) * | 2011-01-14 | 2012-10-04 | Keki Hormusji Gharda | Polymorphism in 5-amino- 1 -(2,6-dichloro-4- trifluoromethylphenyl)-3-cyano-4-trifluoro methyl sulfinyl pyrazole |
| CN102093295A (en) * | 2011-03-10 | 2011-06-15 | 江苏长青农化股份有限公司 | Synthesis method of insecticide Fipronil |
| CN103547572A (en) * | 2011-05-30 | 2014-01-29 | K·H·伽达 | Process for synthesis of fipronil |
| CN103547572B (en) * | 2011-05-30 | 2016-03-30 | K·H·伽达 | A kind of technique of synthesizing ethiprole |
| GB2516446A (en) * | 2013-07-22 | 2015-01-28 | Rotam Agrochem Int Co Ltd | Process for the preparation of n-substituted pyrazole compounds and products of the same |
| CN104557713A (en) * | 2013-10-22 | 2015-04-29 | 江苏托球农化有限公司 | Preparation method of high-purity fipronil |
| CN104557713B (en) * | 2013-10-22 | 2018-08-21 | 江苏托球农化股份有限公司 | High-purity ethiprole preparation method |
| CN104926729A (en) * | 2014-03-18 | 2015-09-23 | 上海泰禾化工有限公司 | Method for synthesis of high-purity fipronil |
| CN104926729B (en) * | 2014-03-18 | 2018-01-19 | 上海泰禾国际贸易有限公司 | A kind of method for synthesizing ethiprole |
| CN106699615A (en) * | 2016-12-28 | 2017-05-24 | 江苏托球农化股份有限公司 | Preparation process of trifluoromethyl sulfinyl chloride |
| CN113825743A (en) * | 2019-03-19 | 2021-12-21 | 格哈达化工有限公司 | Method for synthesizing fipronil |
| CN115650919A (en) * | 2022-04-13 | 2023-01-31 | 华东理工大学 | Method for preparing fipronil from trichloromethyl sulfinyl chloride |
| CN115353490A (en) * | 2022-09-26 | 2022-11-18 | 安徽美诺华药物化学有限公司 | Purification process of fipronil |
| CN115594635A (en) * | 2022-09-29 | 2023-01-13 | 浙江美诺华药物化学有限公司（Cn） | Synthetic method of dechlorinated fipronil |
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Application publication date: 20101208 |