CN1137091C - Prepn. of fenpropathrin - Google Patents
Prepn. of fenpropathrin Download PDFInfo
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- CN1137091C CN1137091C CNB001341561A CN00134156A CN1137091C CN 1137091 C CN1137091 C CN 1137091C CN B001341561 A CNB001341561 A CN B001341561A CN 00134156 A CN00134156 A CN 00134156A CN 1137091 C CN1137091 C CN 1137091C
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Abstract
The present invention relates to a preparation method for fenpropathrin. 2, 2, 3, 3-tetramethylcyclopropylcarboxylic acid and thionyl chloride react to obtain acyl chloride; the acyl chloride further react with a mixture of 3-phenoxy phenylaldehyde, sodium cyanide, triethylamine, water and organic solvent in one step to obtain the fenpropathrin. The present invention has the advantages of mild reaction condition, simple operation, easy control, high yield and product purity and low cost; solid products can be finally obtained, and the present invention is especially suitable for industrialization.
Description
Technical field
The present invention relates to the preparation method of Fenvalerate.
Background technology
Fenvalerate (alpha-cyano-3-phenoxy benzyl-2,2,3,3-Tetramethylcycloprop-ne-ne carboxylic acid methyl esters) be that a new generation has Insecticiding-miticiding specific pyrethroid pesticide, have characteristics such as wide spectrum, efficient, low toxicity, safety, prevent and treat for the worm mite evil of vegetables, fruit, cotton and have special effect.The synthetic method of this compound of having reported mainly contains following several:
(1) from 4-chloro-2,2,3,3-tetramethyl-ring butanone and 3-phenoxy benzaldehyde and potassium cyanide aqueous solution prepared in reaction under 65 ℃ condition.For example: CA 1,122, and 609; US 4,096, and 170; Ger.Offen.2,736,258; The technology that patent provided such as JP79 32,441.
(2) in the presence of phase-transfer catalyst, in sodium cyanide solution, drip 3-phenoxy benzaldehyde and 2,2,3, the method preparation of 3-tetramethyl-ring propyl formyl chloride.For example: CN 1,070, and it is phase-transfer catalyst that 186 (yield is 80-90%) adopt the polyoxyethylene groups ether or the polyoxypropylene base ether of high fatty alcohol, and JP 08,337, and 565 employing triethyl benzyl ammonia chlorides are phase-transfer catalyst.
(3) cyanalcohol of 3-phenoxy benzaldehyde and 2,2,3, the method preparation of 3-tetramethyl-ring propyl formyl chloride reaction.For example Chinese patent CN 1,062,348 technology that provided.
(4) with salt of wormwood with 2,2,3, the 3-Tetramethylcycloprop-ne-ne carboxylic acid becomes sylvite, then it in the presence of phase-transfer catalyst with the acetonitrile reaction of 3-Phenoxyphenyl bromo.Ger.Offen.2 for example, 651,341 technology that provided.
In the preparation method of existing these Fenvalerates, method (1) is although reactions steps is less, and yield is low, and reaction conditions is difficult to carry out suitability for industrialized production; Same quadrat method (2) is although reactions steps is less, and side reaction causes reaction yield low low with product purity more, and product colour is dark; Method (3) is to generate cyanalcohol by the 3-phenoxy benzaldehyde earlier, use 2 again, 2,3,3-tetramethyl-ring propyl formyl chloride acidylate, step is many, total recovery is low, and trivial operations, more outstanding shortcoming are that cyanalcohol is easy to decompose, emit the hydrocyanic acid gas (HCN) of severe toxicity, so the reaction conditions of cyanalcohol and preservation are very harsh; The synthetic difficulty of the raw material 3-Phenoxyphenyl bromo acetonitrile of method (4) is so industrial cost is bigger.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of new Fenvalerate adopts 2,2,3, and 3-tetramethyl-ring propyl formyl chloride and 3-phenoxy benzaldehyde and sodium cyanide single step reaction directly synthesize Fenvalerate.It is compared with present already present method, have yield height, product purity height, cost is low, reaction conditions is gentle, simple to operate, the product characteristics such as (high yield, high-content and product colour are shallow) that are easy to control and can obtain at last solid state, be more suitable in suitability for industrialized production, using.
The present invention is with 2,2,3, and the acyl chlorides that the reaction of 3-Tetramethylcycloprop-ne-ne carboxylic acid and thionyl chloride obtains joins that single step reaction directly obtains Fenvalerate in the mixture of 3-phenoxy benzaldehyde, sodium cyanide, triethylamine, water and organic solvent.
Specific implementation method step of the present invention is:
(1) by 2,2,3, synthetic its acyl chlorides of 3-Tetramethylcycloprop-ne-ne carboxylic acid and thionyl chloride reaction carries out under 14-50 ℃ temperature, and the reaction times is 3-5 hour, and decompression extracts excessive thionyl chloride, and the chrysanthemum acyl chlorides of gained directly uses after with organic solvent dissolution.
(2) in the mixture of 3-phenoxy benzaldehyde and sodium cyanide solution, add a small amount of triethylamine and organic solvent, stir, add above-mentioned chrysanthemum solution of acid chloride then, in-30-80 ℃ scope fully after the reaction, separatory promptly obtains the solution of Fenvalerate, boils off solvent, can obtain the Fenvalerate of solid attitude, product also can obtain pure product through recrystallization.
Employed organic solvent can be an aromatic hydrocarbons among the present invention, as toluene, benzene, dimethylbenzene etc.; Alkane or naphthenic hydrocarbon are as hexanaphthene, normal hexane, Skellysolve A, normal heptane, sherwood oil, gasoline etc.; Ether is as ether, tetrahydrofuran (THF) etc.In the esterification 2,2,3,3-tetramethyl-ring propyl formyl chloride, 3-phenoxy benzaldehyde and sodium cyanide mole number such as can be pressed and add, and sodium cyanide also can suitable excessive 5-30%.Best temperature of reaction is-15-40 ℃.
The present invention has yield height, product purity height, cost is low, reaction conditions is gentle, simple to operate, the product characteristics such as (high yield, high-content and product colour are shallow) that are easy to control and can obtain at last solid state, product yield and content all reach more than 97%, are more suitable in using in suitability for industrialized production.
Embodiment
Embodiment
2,2,3, the preparation method of 3-tetramethyl-ring propyl formyl chloride (being the chrysanthemum acyl chlorides): in the round-bottomed flask that has induction stirring, add 1mol 2,2,3,3-Tetramethylcycloprop-ne-ne carboxylic acid and 1.1mol thionyl chloride, under 14 ℃ temperature, stirred 4 hours, under 40 ℃ temperature, stir half an hour, extract excessive thionyl chloride with water pump then.The chrysanthemum acyl chlorides that obtains directly uses with toluene dissolving back.
In three mouthfuls of reaction flasks, add 99%3-phenoxy benzaldehyde (62.5mmol), 95% sodium cyanide (3.88g), water and toluene dissolving and drip triethylamine a little.At normal temperatures, add 2,2,3, the toluene solution of 3-tetramethyl-ring propyl formyl chloride (65.8mmol).Stir, after fully reacting completely, separatory.Use anhydrous magnesium sulfate drying, filter, boil off solvent, get white solid, yield is 97.5%, and content is 98.0%.Recrystallization gets pure product again.
Claims (2)
1. the preparation method of a Fenvalerate is characterized in that it comprises the steps:
(1) with 2,2,3,3-Tetramethylcycloprop-ne-ne carboxylic acid and thionyl chloride reacted 3-4 hour under 14-50 ℃ temperature, and decompression extracts excessive thionyl chloride, got the chrysanthemum solution of acid chloride;
(2) in the mixture of 3-phenoxy benzaldehyde organic solvent solution and sodium cyanide solution, add a little triethylamine, stir, add above-mentioned chrysanthemum solution of acid chloride then, after fully reacting completely under-30-80 ℃, separatory boils off solvent, obtain the solid Fenvalerate, recrystallization obtains pure product.
2. according to the preparation method of the described Fenvalerate of claim 1, it is characterized in that described organic solvent is toluene, benzene, dimethylbenzene, hexanaphthene, normal hexane, Skellysolve A, normal heptane, sherwood oil, gasoline, ether or tetrahydrofurane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001341561A CN1137091C (en) | 2000-12-06 | 2000-12-06 | Prepn. of fenpropathrin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001341561A CN1137091C (en) | 2000-12-06 | 2000-12-06 | Prepn. of fenpropathrin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1357538A CN1357538A (en) | 2002-07-10 |
| CN1137091C true CN1137091C (en) | 2004-02-04 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001341561A Expired - Fee Related CN1137091C (en) | 2000-12-06 | 2000-12-06 | Prepn. of fenpropathrin |
Country Status (1)
| Country | Link |
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| CN (1) | CN1137091C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101017165B (en) * | 2007-03-09 | 2011-04-27 | 中国水产科学研究院淡水渔业研究中心 | Method for preparing fenpropathrin artificial antigen |
| CN106918705B (en) * | 2017-01-22 | 2023-06-13 | 贵州勤邦食品安全科学技术有限公司 | Test paper for detecting fenpropathrin and application thereof |
| CN116354850B (en) * | 2023-03-23 | 2024-02-13 | 大连凯飞化学股份有限公司 | Preparation method of fenpropathrin |
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2000
- 2000-12-06 CN CNB001341561A patent/CN1137091C/en not_active Expired - Fee Related
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| Publication number | Publication date |
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| CN1357538A (en) | 2002-07-10 |
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Granted publication date: 20040204 Termination date: 20121206 |