CN1090611C - 3-bromo-4-fluoro methylbenzene process of cyhalofop-butyl production - Google Patents
3-bromo-4-fluoro methylbenzene process of cyhalofop-butyl production Download PDFInfo
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- CN1090611C CN1090611C CN99117035A CN99117035A CN1090611C CN 1090611 C CN1090611 C CN 1090611C CN 99117035 A CN99117035 A CN 99117035A CN 99117035 A CN99117035 A CN 99117035A CN 1090611 C CN1090611 C CN 1090611C
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Abstract
The present invention relates to a method for producing cypermethrin (cyfluthrin) by a method of 3-bromine-4-fluorotoluene. The 3-bromine-4-fluorotoluene and oxybenzene are used as a raw material to obtain a cypermethrin product by the reactions of condensation, chlorination, hydrolysis and esterification. The present invention has the advantages of stepwise synthesis for a production process, reasonable technological lines, moderate and feasible technological conditions, high total yield of the product, high contents and low integrated cost of production, and has favorable economical benefit and social benefit; the present invention provides pesticide with broad spectra, high efficiency and low toxicity for agricultural production.
Description
The present invention relates to a kind of production method of pyrethrin, particularly a kind of method of 3-bromo-4-toluene fluoride method production cyfloxylate.
In the prior art, cyfloxylate is the pyrethroid insecticide of a kind of wide spectrum, efficient, low toxicity, generally respectively is called: Cyfluthrin; Chemical name is: 2, and 2-dimethyl-3-(2, the 2-dichloroethylene)-cyclopropane-carboxylic acid-a-cyano group-3-phenoxy group-4-fluoro-methylbenzyl ester; Molecular formula: C
22H
18Cl
2FNO
3Cyfloxylate is widely used in the various agricultural chemicals of allotment, mainly adopts parachlorotoluene, para-totuidine, fluorobenzene to synthesize, and merits and demerits is respectively being arranged aspect technology controlling and process and the yield.
The production method that the purpose of this invention is to provide a kind of new cyfloxylate, creating with 3-bromo-4-toluene fluoride is starting raw material synthetic novel process, improves the product recovery rate, reduces production costs, and enlarges pesticide material production, satisfies the agriculture production needs.
Purpose of the present invention can realize by following technical measures: this production method is a raw material with 3-bromo-4-toluene fluoride and phenol, after the condensation reaction, obtains the fluorine m-phenoxytoluene through washing, extraction, distillation; After chlorination, precipitation must be to fluorine m-phenoxy benzyl chloride to the fluorine m-phenoxytoluene; After fluorine m-phenoxy benzyl chloride added the hexamethylenetetramine hydrolysis, through distill 3-phenoxy group-4-fluorobenzaldehyde; 3-phenoxy group-4-fluorobenzaldehyde and sodium cyanide solution add DV chrysanthemum acyl chlorides after esterification, and precipitation obtains cyfloxylate.Its reaction process is as follows:
(1) synthetic to the fluorine m-phenoxytoluene
(2) synthetic to fluorine m-phenoxy benzyl chloride
(3) synthetic 3-phenoxy group-4-fluorobenzaldehyde
(4) synthetic cyfloxylate
Production technique of the present invention is provided by the following drawings:
Fig. 1 is a process flow diagram of the present invention.
The invention will be further described below with reference to accompanying drawing:
(1) synthetic to the fluorine m-phenoxytoluene
Yield, the content of present method the first step condensation reaction gained intermediates depend on material proportion, solvent, catalyzer and processing parameter condition.The our factory is by test, average yield＞80%, content＞98.5%.
Embodiment one: in the flask that has agitator, add solvent phenol 141.2g (1.5mol) or N, and dinethylformamide, sodium hydroxide 60g (1.5mol) and toluene 500ml mix, and boiling dewaters; Add solvent 150ml and catalyzer 0.5g, be heated to 140～145 ℃, add 3-bromo-4-toluene fluoride 94.2g (0.5mol), stirred 4 hours, through washing, petroleum ether extraction, 94～96 ℃/267Pa cut, yield 81%, content 98.2% are collected in distillation.
(2) synthetic to fluorine m-phenoxy benzyl chloride
Second step was a chlorination reaction, and material feeds chlorine and reacts under the certain temperature state, and average yield is 95%, and average content is 94.0%.
Embodiment two: add in the flask of being furnished with thermometer, agitator, gas introduction tube, reflux exchanger fluorine m-phenoxytoluene 100g (0.495mol), catalyzer 5g, tetracol phenixin 1000g, heat temperature raising to 80～100 ℃, a certain amount of chlorine of back feeding makes it slowly to reflux, after reaching home, be incubated postcooling half an hour again, decompression steams solvent and obtains fluorine m-phenoxy benzyl chloride.Yield 95%, content (chlorinated mixture): 95.5%.
(3) synthetic 3-phenoxy group-4-fluorobenzaldehyde
The reaction of the 3rd one-step hydrolysis improves yield, content by control material proportion, solution pH value and temperature, time.
Embodiment three: add the glacial acetic acid solution of 118.25g (0.5mol) to fluorine m-phenoxy benzyl chloride, 280g (1mol) hexamethylenetetramine and 500ml50% to the flask of being furnished with thermometer, agitator, gas introduction tube, reflux exchanger, quicken to stir, heat temperature raising to 104～108 ℃ or under related solvents back flow reaction, refluxed 4 hours, be chilled to room temperature, drip the 200ml concentrated hydrochloric acid, refluxed 15 minutes, reaction finishes, with toluene extractive reaction liquid, through alkali cleaning, washing, steam and remove toluene, 122～124 ℃/0.02KPa, yield 91%, content 97.3% are collected in distillation.
(4) synthetic cyfloxylate
The 4th step esterification and must product in the presence of phase-transfer catalyst.
Embodiment four: in there-necked flask, add 3-phenoxy group-4-fluorobenzaldehyde (97%) 220g (1mol), 20%NaCN aqueous solution 300g, 1000ml hexanaphthene and catalyzer 2g successively, be cooled to 0-15 ℃, begin to drip DV chrysanthemum acyl chlorides 245g with ice bath, drip continuation 15～20 ℃ of reactions 6-10 hour, reaction finishes, through layering, alkali cleaning, be washed to neutrality, last atmospheric and vacuum distillation, reclaim solvent, get cyfloxylate, yield 93.8%, content 90.0%.
The present invention is a starting raw material with 3-bromo-4-toluene fluoride, carry out the stepwise synthesis cyfloxylate, synthesis route is reasonable, the processing condition gentleness is feasible, the total yield of products height, and content is higher, the production comprehensive cost is low, good in economic efficiency, for pesticide producing provides the former medicine of wide spectrum, efficient, low toxicity, support agricultural development.
Claims (5)
1. the method for a 3-bromo-4-toluene fluoride method production cyfloxylate, it is characterized in that with 3-bromo-4-toluene fluoride and phenol be raw material, must be through condensation to the fluorine m-phenoxytoluene, must be to fluorine m-phenoxy benzyl chloride to this oxygen base toluene between fluorine through chlorination, fluorine m-phenoxy benzyl chloride is added the hexamethylenetetramine hydrolysis get 3-phenoxy group-4-fluorobenzaldehyde, add DV chrysanthemum acyl chlorides in 3-phenoxy group-4-fluorobenzaldehyde and the sodium cyanide solution and obtain cyfloxylate through esterification, its reaction process is as follows:
(1) synthetic to the fluorine m-phenoxytoluene
(2) synthetic to fluorine m-phenoxy benzyl chloride
(3) synthetic 3-phenoxy group-4-fluorobenzaldehyde
(4) synthetic cyfloxylate
2. method according to claim 1 is characterized in that synthetic reaction to the fluorine m-phenoxytoluene, and the material Heating temperature is 140～145 ℃, and solvent is N, dinethylformamide or phenol.
3. method according to claim 1 is characterized in that synthetic reaction to fluorine m-phenoxy benzyl chloride, and the material Heating temperature is 80～100 ℃.
4. method according to claim 1 is characterized in that the reaction of synthetic 3-phenoxy group-4-fluorobenzaldehyde, the material Heating temperature be 104～108 ℃ or under related solvents back flow reaction.
5. method according to claim 1 is characterized in that material is cooled to 0～15 ℃ of dropping, 15～20 ℃ of insulations in the reaction of synthetic cyfloxylate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99117035A CN1090611C (en) | 1999-08-18 | 1999-08-18 | 3-bromo-4-fluoro methylbenzene process of cyhalofop-butyl production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99117035A CN1090611C (en) | 1999-08-18 | 1999-08-18 | 3-bromo-4-fluoro methylbenzene process of cyhalofop-butyl production |
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| Publication Number | Publication Date |
|---|---|
| CN1244521A CN1244521A (en) | 2000-02-16 |
| CN1090611C true CN1090611C (en) | 2002-09-11 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN99117035A Expired - Fee Related CN1090611C (en) | 1999-08-18 | 1999-08-18 | 3-bromo-4-fluoro methylbenzene process of cyhalofop-butyl production |
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116410070A (en) * | 2021-12-31 | 2023-07-11 | 江苏优嘉植物保护有限公司 | Production process of p-fluoro-m-phenoxy benzaldehyde |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4287208A (en) * | 1979-07-18 | 1981-09-01 | Bayer Aktiengesellschaft | Combating arthropods with stereoisomers of 2,2-dimethyl-3-(2,2-dichlorovinyl)-cyclopropane-1-carboxylic acid α-c |
| US4350640A (en) * | 1979-08-18 | 1982-09-21 | Bayer Aktiengesellschaft | Preparation of substituted (cyclo)alkanecarboxylic acid α-cyano-3-phenoxy-benzyl esters |
-
1999
- 1999-08-18 CN CN99117035A patent/CN1090611C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4287208A (en) * | 1979-07-18 | 1981-09-01 | Bayer Aktiengesellschaft | Combating arthropods with stereoisomers of 2,2-dimethyl-3-(2,2-dichlorovinyl)-cyclopropane-1-carboxylic acid α-c |
| US4350640A (en) * | 1979-08-18 | 1982-09-21 | Bayer Aktiengesellschaft | Preparation of substituted (cyclo)alkanecarboxylic acid α-cyano-3-phenoxy-benzyl esters |
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