CN100358858C - Method for preparing lefluthrin - Google Patents
Method for preparing lefluthrin Download PDFInfo
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- CN100358858C CN100358858C CNB200510015836XA CN200510015836A CN100358858C CN 100358858 C CN100358858 C CN 100358858C CN B200510015836X A CNB200510015836X A CN B200510015836XA CN 200510015836 A CN200510015836 A CN 200510015836A CN 100358858 C CN100358858 C CN 100358858C
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- tefluthrin
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- tetrafluoro
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- methyl
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Abstract
The present invention discloses a method for preparing tefluthrin, which belongs to the preparative technique of the tefluthrin. The method comprises the following procedures: acid amide organic matter of which the dosage is 3 times to 20 times as much as the quality of 2, 3, 5, 6-p-methyltertafluorobenzyl chloride; the equally molar 2, 5, 6-p-methyltertafluorobenzyl chloride and cis-3-(2-chloro-3, 3, 3-trifluoro-1-propenyl)-2 is used as solvent, 2-dimethylcyclopropane carboxylate acid are added in the solvent, and acid-binding agents of which the dosage is 1 time to 5 times as much as the amount of the substance of the 2, 3, 5, 6-p-methyltertafluorobenzyl chloride are also added in the solvent; the solvent reacts through stirring for 30 hours to 60 hours at the temperature of 20DEG. C to 60DEG. C; then, extraction agents of which the dosage is 6 times to 40 times as much as the quality of the 2, 3, 5, 6-p-methyltertafluorobenzyl chloride and water of which the dosage is equal to the dosage of the extraction agents are added in the solvent; the solvent is divided so that an organic phase is extracted and the extraction agents are evaporated and removed, so a product is obtained. The present invention has the advantages that reaction process is simple, cost is low, operational condition is mild, a yield of reaction is over 90 percent, product purity is over 96 percent, and the present invention is suitable for large industrial production.
Description
Technical field
The invention relates to the new preparation method of tefluthrin, belong to the technology of preparing of tefluthrin.
Background technology
Tefluthrin is a kind of important pyrethroid pesticide, mainly as soil insecticide.The synthetic route of tefluthrin mainly is that the 6-tetrafluoro is a raw material to xylyl alcohol with time acid and 2,3,5, and concrete synthetic route has two kinds:
Method one:
Time acid (1) obtains time isoxazolecarboxylic acid (2) through chloride, and time isoxazolecarboxylic acid (2) is again with 2,3,5, and the 6-tetrafluoro to xylyl alcohol (3) esterification takes place and obtains tefluthrin (4).
This route existed in synthesizing of time isoxazolecarboxylic acid, need remove unnecessary sulfur oxychloride, and its method adopts distillation usually and realized with the methylbenzene azeotropic backflow, purification difficult, and also time isoxazolecarboxylic acid poor stability influences next step reaction yield and purity.Time isoxazolecarboxylic acid (2) and 2,3,5, the 6-tetrafluoro need the higher pyridine of price as acid binding agent usually, and aftertreatment needs pickling to the esterification of xylyl alcohol (3), method such as alkali cleaning or column chromatography is extracted, the process complexity, thus limited suitability for industrialized production (GB2066810A, 1981-07-15).
Method two:
This method is used dicyclohexylcarbodiimide (DCC) and 4-Dimethylamino pyridine (DMAP), and dicyclohexylcarbodiimide (DCC) costs an arm and a leg, and cannot reclaim, and has limited industrial production.(Yao Guangyuan, the study on the synthesis of tefluthrin: [master thesis], Tianjin; University Of Tianjin, 2004)
Summary of the invention
The object of the present invention is to provide a kind of preparation method of tefluthrin, it is simple that this method has technology, and production cost is low, the high and high characteristics of purity of product yield.
This programme is realized that by following technical proposals a kind of preparation method of tefluthrin is characterized in that comprising following process:
Be 2,3,5 with consumption, the 6-tetrafluoro is in the solvent to 3～20 times amides organism of the quality of methyl-benzyl chlorine, adds 2,3 of equimolar amount, 5, the 6-tetrafluoro is to methyl-benzyl chlorine and time acid, and the adding consumption is 2,3,5, the 6-tetrafluoro is to the acid binding agent of 1～5 times of the amount of methyl-benzyl chloride material, under 20～60 ℃, stirring reaction 30～60 hours, adding consumption again is 2,3,5, the 6-tetrafluoro to 6～40 times extraction agent of methyl-benzyl chlorine quality and with the water of extraction agent equivalent, through separatory, get organic phase and steam except that extraction agent, promptly get product, yield 90%～96%, purity is greater than 96%.
Above-mentioned amide solvent is N, dinethylformamide or N,N-dimethylacetamide;
Above-mentioned acid binding agent is yellow soda ash, sodium bicarbonate or sodium hydroxide.
Above-mentioned extraction agent is methylene dichloride, trichloromethane, ethyl acetate, sherwood oil or benzene.
The technology that the invention has the advantages that reaction is simple, and cost is low, the operational condition gentleness, and reaction yield is greater than 90%, and product purity is applicable to big industrial production greater than 96%.
Embodiment
Example 1:
18.15g time acid, 15.94g 2,3,5, the 6-tetrafluoro is dissolved in 375mLN to methyl-benzyl chlorine and 1.26g sodium bicarbonate, and in the dinethylformamide, 10 ℃ were reacted 60 hours down, respectively with the ethyl acetate of 500mL and the water dilute reaction solution of 500mL, and separatory.Steam and remove ethyl acetate, obtain light yellow solid tefluthrin 28.80g, yield 91.86%, purity 96.29%.
Product
1H NMR analytical data is as follows:
1H?NMRδ(CDCl
3)，300MHz：6.89(1H，d，J
AB＝9.0Hz，H
A)，2.18(1H，t，J
AB＝9.0Hz，J
BC＝9.0Hz，H
B)，1.98(1H，d，J
BC＝9.0Hz，H
C)，1.29(6H，s，H
D)，5.17(1H，s，J＝12Hz，H
E)，5.24(1H，s，J＝12Hz，H
F)，2.29(3H，s，H
G)。
Example 2:
18.15g time acid, 15.94g 2,3,5, the 6-tetrafluoro is dissolved in 200mLN to methyl-benzyl chlorine and 12.60g sodium bicarbonate, and in the dinethylformamide, 25 ℃ were reacted 40 hours down, respectively with the trichloromethane of 400mL and the water dilute reaction solution of 400mL, and separatory.Steam and remove trichloromethane, obtain light yellow solid tefluthrin 29.10g, yield 92.82%, purity 96.13%.
Example 3:
18.15g time acid, 15.94g 2,3,5, the 6-tetrafluoro is dissolved in 375mLN to methyl-benzyl chlorine and 12.60g sodium bicarbonate, and in the N-N,N-DIMETHYLACETAMIDE, 35 ℃ were reacted 30 hours down, respectively with the trichloromethane of 300mL and the water dilute reaction solution of 300mL, and separatory.Steam and remove trichloromethane, obtain light yellow solid tefluthrin 28.67g, yield 91.45%, purity 96.56%.
Example 4:
18.15g time acid, 15.94g 2,3,5, the 6-tetrafluoro is dissolved in 300mLN to methyl-benzyl chlorine and 12.60g sodium bicarbonate, and in the dinethylformamide, 40 ℃ were reacted 48 hours down, respectively with the trichloromethane of 200mL and the water dilute reaction solution of 200mL, and separatory.Steam and remove trichloromethane, obtain light yellow solid tefluthrin 29.01g, yield 92.52%, purity 96.59%.
Example 5:
18.15g time acid, 15.94g 2,3,5, the 6-tetrafluoro is dissolved in 240mLN to methyl-benzyl chlorine and 9.45g sodium bicarbonate, and in the N-N,N-DIMETHYLACETAMIDE, 60 ℃ were reacted 36 hours down, respectively with the methylene dichloride of 500mL and the water dilute reaction solution of 500mL, and separatory.Steam and remove methylene dichloride, obtain light yellow solid tefluthrin 29.25g, yield 93.30%, purity 96.48%.
Example 6:
18.15g time acid, 15.94g 2,3,5, the 6-tetrafluoro is dissolved in 100mLN to methyl-benzyl chlorine and 15.9g yellow soda ash, and in the dinethylformamide, 30 ℃ were reacted 48 hours down, respectively with the sherwood oil of 100mL and the water dilute reaction solution of 100mL, and separatory.Steam and remove sherwood oil, obtain light yellow solid tefluthrin 28.75g, yield 91.70%, purity 96.02%.
Claims (4)
1. the preparation method of a tefluthrin, it is characterized in that comprising following process: at consumption is 2,3,5, the 6-tetrafluoro is in the solvent to 3～20 times amides organism of the quality of methyl-benzyl chlorine, adds 2 of equimolar amount, 3,5, the 6-tetrafluoro is to methyl-benzyl chlorine and time acid, and the adding consumption is 2,3,5, the 6-tetrafluoro is to the acid binding agent of 1～5 times of the amount of methyl-benzyl chloride material, under 20～60 ℃, stirring reaction 30～60 hours, adding consumption again is 2,3,5, the 6-tetrafluoro to 6～40 times extraction agent of methyl-benzyl chlorine quality and with the water of extraction agent equivalent, through separatory, get organic phase and steam except that extraction agent, make tefluthrin.
2. by the preparation method of the described tefluthrin of claim 1, it is characterized in that amide solvent is N, dinethylformamide or N,N-dimethylacetamide.
3. by the preparation method of the described tefluthrin of claim 1, it is characterized in that acid binding agent is yellow soda ash, sodium bicarbonate or sodium hydroxide.
4. by the preparation method of the described tefluthrin of claim 1, it is characterized in that extraction agent is methylene dichloride, trichloromethane, ethyl acetate, sherwood oil or benzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200510015836XA CN100358858C (en) | 2005-11-01 | 2005-11-01 | Method for preparing lefluthrin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200510015836XA CN100358858C (en) | 2005-11-01 | 2005-11-01 | Method for preparing lefluthrin |
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|---|---|
| CN1760168A CN1760168A (en) | 2006-04-19 |
| CN100358858C true CN100358858C (en) | 2008-01-02 |
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| CNB200510015836XA Expired - Fee Related CN100358858C (en) | 2005-11-01 | 2005-11-01 | Method for preparing lefluthrin |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103444765A (en) * | 2012-05-31 | 2013-12-18 | 陕西汤普森生物科技有限公司 | Dicyclanil and pyrethroid-containing insecticidal composition |
| AU2017203635B2 (en) * | 2017-05-30 | 2022-02-03 | Rotam Agrochem International Company Limited | A novel crystalline form of tefluthrin, a process for its preparation and use of the same |
| US11739045B1 (en) * | 2022-02-22 | 2023-08-29 | Rotam Agrochem International Company Limited | Crystal of tefluthrin, preparation method therefor and use thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4405640A (en) * | 1979-12-21 | 1983-09-20 | Imperial Chemical Industries Plc | Substituted fluorobenzyl cyclopropane carboxylates useful as insecticides |
-
2005
- 2005-11-01 CN CNB200510015836XA patent/CN100358858C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4405640A (en) * | 1979-12-21 | 1983-09-20 | Imperial Chemical Industries Plc | Substituted fluorobenzyl cyclopropane carboxylates useful as insecticides |
Non-Patent Citations (1)
| Title |
|---|
| 七氟菊酯的合成研究. 姚光源.天津大学硕士学位论文. 2003 * |
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| CN1760168A (en) | 2006-04-19 |
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