CN102060774A - Method for synthesizing fipronil - Google Patents
Method for synthesizing fipronil Download PDFInfo
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- CN102060774A CN102060774A CN2009102197761A CN200910219776A CN102060774A CN 102060774 A CN102060774 A CN 102060774A CN 2009102197761 A CN2009102197761 A CN 2009102197761A CN 200910219776 A CN200910219776 A CN 200910219776A CN 102060774 A CN102060774 A CN 102060774A
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- synthesizing
- fipronil
- phenyl
- amino
- worm nitrile
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Abstract
The invention relates to a method for synthesizing pesticide, in particular to a method for synthesizing fipronil and provides a method for synthesizing fipronil having the characteristics of simplicity in operation, mild condition, high yield and environmental friendliness. In the technical scheme, fipronil is synthesized by a catalytic oxidation method. The method comprises the following steps of: synthesizing 5-amino-3-cyan-1-(2,6-dichloro-4-trifluoro methyl-phenyl)-4-sulfur cyan-pyrazol; synthesizing a disulfide; synthesizing 5-amino-3-cyan-1-(2,6-dichloro-4-trifluoro methyl-phenyl)-4-fluoroform-sulfenyl-pyrazol; and synthesizing the fipronil.
Description
Technical field:
The present invention relates to a kind of synthetic method of agricultural chemicals, more particularly, relate to the synthetic method of fluorine worm nitrile.
Background technology:
Thoroughly stop production, circulation and the use of 5 kinds of high malicious organophosphorus pesticides from January 9th, 2008 in China, the thorough forbidding of riskiest pesticide has caused the vacancy in the sterilant supply, is badly in need of more than 10 ten thousand t and substitutes agricultural chemicals and remedy this vacancy.The development need of pesticide industry is dealt with the disease and pest that emerges in an endless stream by a large amount of research and development inputs, releases new product as required to adapt to the social development requirement to food safety and environmental protection pay attention to day by day.The transfer of the whole world developing country of agricultural chemicals headed by the China, bring valuable technology input and globalizing market chance to Chinese Enterprise, have technology and environment-friendly advantage, the agricultural chemicals of producing low toxicity, low pollution kind will face the historic opportunity that share of market improves fast.
Fluorine worm nitrile and azoxystrobin compound can enhanced activity, are applicable to cereal, paddy rice, grape, fruit, banana, soybean, vegetables, lawn and ornamental plant.Fluorine worm nitrile is harmless to beneficial organism, and is environmentally friendly, and the rampant again risk of no insect will play a significant role in the insect innoxious governance.
Fluorine worm nitrile, chemistry 5-amino by name-3-cyano group-1-(2,6-dichlor-4-trifluoromethyl-phenyl)-4-trifluoromethyl sulfinyl pyrazole, structural formula is as shown below.
Fluorine worm nitrile
Present stage mainly contains two kinds of methods to fluorine worm nitrile synthetic:
1.5-amino-3-cyano group-1-(2,6-dichlor-4-trifluoromethyl-phenyl) reaction of pyrazoles and trifluoromethyl sulphur chlorine generates 5-amino-3-cyano group-1-(2,6-dichlor-4-trifluoromethyl-phenyl)-4-trifluoromethylthio pyrazoles, and then obtain fluorine worm nitrile with hydrogen peroxide or metachloroperbenzoic acid oxidation.In this route, trifluoromethyl sulphur chlorine toxicity is very high, and is gas, thereby operational condition is required high in industrial application;
2. with the little CF of toxicity
3SOCl or CF
3SONR
2The trifluoromethyl sulphur chlorine that replaces high poison, direct and 5-amino-3-cyano group-1-(2,6-dichlor-4-trifluoromethyl-phenyl) pyrazoles generates fluorine worm nitrile by single step reaction, though this method has reduced the pollution to environment, removed oxidation step from, yet the synthetic yield is lower.
Summary of the invention:
The present invention is exactly at the problems referred to above, and the synthetic method of a kind of simple to operate, mild condition, pollution is little, yield is high fluorine worm nitrile is provided.
In order to realize above-mentioned purpose of the present invention, the present invention adopts following technical scheme, utilizes catalytic oxidation that fluorine worm nitrile is synthesized, and method steps is:
1.5-amino-3-cyano group-1-(2,6-dichlor-4-trifluoromethyl-phenyl)-4-thiocyanogen-pyrazoles is synthetic
Reaction equation is:
2. disulphide is synthetic
Reaction equation is:
3.5-amino-3-cyano group-1-(2,6-dichlor-4-trifluoromethyl-phenyl)-4-trifluoromethylthio one pyrazoles is synthetic
Reaction equation is:
4. fluorine worm nitrile is synthetic
Reaction equation is:
Beneficial effect of the present invention:
1. the present invention is simple to operate, and the reaction conditions gentleness is little to the pollution of environment;
2. yield of the present invention is 95.7%.
Embodiment:
Method steps of the present invention is:
1.5-amino-3-cyano group-1-(2,6-dichlor-4-trifluoromethyl-phenyl)-4-thiocyanogen-pyrazoles is synthetic
Reaction equation is:
2. disulphide is synthetic
Reaction equation is:
3.5-amino-3-cyano group-1-(2,6-dichlor-4-trifluoromethyl-phenyl)-4-trifluoromethylthio one pyrazoles is synthetic
Reaction equation is:
4. fluorine worm nitrile is synthetic
Reaction equation is:
The structure of end product of the present invention has obtained the affirmation of infrared spectrum and nuclear magnetic spectrogram, and spectral data is as follows: IR 1761 (C=O), 1697 (C=C), 3068 (C-H), 1637 (C-N).
HNMR(CDCl
3，400MHz)1.11(s，6H，CH
3)，3.57(s，4H，CH
2)，8.53(s，1H，pY-H)。
13CNMR(CDCl
3，100MHz)16.2，48.1，120.6，126.1，139.4，140.8，151.3。
Claims (1)
1. the synthetic method of fluorine worm nitrile is characterized in that, the present invention adopts following technical scheme, utilizes catalytic oxidation that fluorine worm nitrile is synthesized, and method steps is:
(1) 5-amino-3-cyano group-1-(2,6-dichlor-4-trifluoromethyl-phenyl)-4-thiocyanogen-pyrazoles is synthetic
Reaction equation is:
(2) disulphide is synthetic
Reaction equation is:
(3) 5-amino-3-cyano group-1-(2,6-dichlor-4-trifluoromethyl-phenyl)-4-trifluoromethylthio one pyrazoles is synthetic
Reaction equation is:
(4) fluorine worm nitrile is synthetic
Reaction equation is:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102197761A CN102060774A (en) | 2009-11-11 | 2009-11-11 | Method for synthesizing fipronil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102197761A CN102060774A (en) | 2009-11-11 | 2009-11-11 | Method for synthesizing fipronil |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102060774A true CN102060774A (en) | 2011-05-18 |
Family
ID=43996298
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009102197761A Pending CN102060774A (en) | 2009-11-11 | 2009-11-11 | Method for synthesizing fipronil |
Country Status (1)
| Country | Link |
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| CN (1) | CN102060774A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102690232A (en) * | 2012-05-30 | 2012-09-26 | 河南中医学院 | Synthesizing method for fipronil intermediates |
| CN103360316A (en) * | 2013-04-22 | 2013-10-23 | 浙江海正化工股份有限公司 | Preparation method of fipronil |
| CN107033044A (en) * | 2017-06-13 | 2017-08-11 | 江苏凌云药业股份有限公司 | A kind of preparation method to trifluoromethylthio phenol |
| CN109696548A (en) * | 2017-10-23 | 2019-04-30 | 北京维德维康生物技术有限公司 | A kind of kit and its preparation method and application detecting Fipronil |
| CN114213330A (en) * | 2021-12-29 | 2022-03-22 | 天和药业股份有限公司 | Method for treating fipronil refining mother liquor |
| WO2023279671A1 (en) * | 2021-07-05 | 2023-01-12 | 浙江海正药业股份有限公司 | Method for synthesizing fipronil intermediate |
-
2009
- 2009-11-11 CN CN2009102197761A patent/CN102060774A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102690232A (en) * | 2012-05-30 | 2012-09-26 | 河南中医学院 | Synthesizing method for fipronil intermediates |
| CN103360316A (en) * | 2013-04-22 | 2013-10-23 | 浙江海正化工股份有限公司 | Preparation method of fipronil |
| CN107033044A (en) * | 2017-06-13 | 2017-08-11 | 江苏凌云药业股份有限公司 | A kind of preparation method to trifluoromethylthio phenol |
| CN107033044B (en) * | 2017-06-13 | 2019-02-12 | 江苏凌云药业股份有限公司 | A kind of preparation method of pair of trifluoromethylthio phenol |
| CN109696548A (en) * | 2017-10-23 | 2019-04-30 | 北京维德维康生物技术有限公司 | A kind of kit and its preparation method and application detecting Fipronil |
| WO2023279671A1 (en) * | 2021-07-05 | 2023-01-12 | 浙江海正药业股份有限公司 | Method for synthesizing fipronil intermediate |
| CN114213330A (en) * | 2021-12-29 | 2022-03-22 | 天和药业股份有限公司 | Method for treating fipronil refining mother liquor |
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Application publication date: 20110518 |