CN1239473C - Fenvalerate preparing process - Google Patents
Fenvalerate preparing process Download PDFInfo
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- CN1239473C CN1239473C CN 200310106703 CN200310106703A CN1239473C CN 1239473 C CN1239473 C CN 1239473C CN 200310106703 CN200310106703 CN 200310106703 CN 200310106703 A CN200310106703 A CN 200310106703A CN 1239473 C CN1239473 C CN 1239473C
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Abstract
The present invention relates to a preparation method for fenvalerate. The preparation method uses triethylamine as a catalyst; and 2-(4-chlorophenyl)-3-methylbutanoic acid and thionyl chloride react to obtain acyl chloride which further reacts with a mixture of 3-phenoxy phenylaldehyde, sodium cyanide, triethylamine, water and organic solvent to obtain the fenvalerate of an agricultural chemical. Compared with the present method, the preparation method has the advantages of high yield, high product purity, low cost, mild reaction condition, simple operation, easy of reaction control, etc. The content of original drugs reaches more than 95 %, the yield reaches more than 97 %, and the preparation method is suitable for being used in a commercial process.
Description
Technical field
The present invention relates to the preparation method of fenvalerate, it is to adopt triethylamine to make catalyzer, 2-(4-chloro-phenyl-)-3 Methylbutanoic acid and thionyl chloride are reacted the acyl chlorides that obtains, and the mixture single step reaction with 3-phenoxy benzaldehyde, sodium cyanide, triethylamine, water and organic solvent obtains the fenvalerate agricultural chemicals again.
Background technology
Fenvalerate [(R, S)-2-(4-chloro-phenyl-)-3 Methylbutanoic acid-(±)-alpha-cyano-3-phenoxy group benzyl ester] be SUMITOMO CHEMICAL chemical industrial company in 1974 research and development a kind of efficient, wide spectrum, light is stable and the pyrethroid insecticides of low residue, pest control for cotton, vegetables, fruit, tobacco, corn and potato etc. has special effect, its drug effect can be suitable with Cypermethrin, but its synthesis technique is simple than Cypermethrin, raw material is easy to solve, and production cost is low.The synthetic method of this compound of having reported mainly contains following several:
(1) α-carboxyl-3-phenoxy group benzylalcohol and 2-(4-chloro-phenyl-)-3-methylbutyryl chlorine reaction generates 2-(4-chloro-phenyl-)-3 Methylbutanoic acid-α-carboxyl-3-phenoxy group benzyl ester, again through amidation and dewater fenvalerate.For example: the technology that patent provided such as day clear 53-59646 of the disclosure and day clear 53-59642 of the disclosure and day clear 53-59643 of the disclosure.
(2) in the presence of phase-transfer catalyst, the method preparation of sodium cyanide and 3-phenoxy benzaldehyde and 2-(4-chloro-phenyl-)-3-methylbutyryl chlorine reaction.For example: U.S. Pat 4,110,363 employing macrocyclic crown ethers are phase-transfer catalyst, it is phase-transfer catalyst that Canadian Patent CA 1123003 adopts Tetrabutyl amonium bromides.
(3) the method preparation of α-Qing Ji-3-Ben Yangjibianchun and 2-(4-chloro-phenyl-)-3-methylbutyryl chlorine reaction.The technology that provided of clear 49-26425 and the clear 61-68458 of day disclosure for example.
(4) 2-(4-chloro-phenyl-)-3 Methylbutanoic acid sodium and alpha-cyano-3-phenoxy group benzyl bromine reacts in the dinethylformamide in the presence of phase-transfer catalyst or at N.The technology that provided of clear 52-62238 and the clear 51-43740 of day disclosure for example.
(5) reaction of 2-(4-chloro-phenyl-)-3-methylbutyryl bromine and 3-phenoxy benzaldehyde obtains 2-(4-chloro-phenyl-)-3 Methylbutanoic acid-alpha-brominated-3-phenoxy group benzyl ester, again with sodium cyanide in the presence of phase-transfer catalyst, react fenvalerate.For example: U.S. Pat 4,360,478 technology that provided.
In the preparation method of above-mentioned fenvalerate, method (1) reactions steps is more, is mainly used in the fenvalerate of preparation optically active; 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-(4-chloro-phenyl-)-3-methylbutyryl chlorine acidylate again, step is many, total recovery is low, trivial operations, more outstanding shortcoming is that cyanalcohol is easy to decompose, and emits 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 alpha-cyano of method (4)-3-phenoxy group benzyl bromine is so industrial cost is bigger; Method (5) is a first step long reaction time, trivial operations, and total recovery is low.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of new fenvalerate can overcome the shortcoming of prior art.Adopt triethylamine to make catalyzer, the directly synthetic fenvalerate of 2-(4-chloro-phenyl-)-3-methylbutyryl chlorine and 3-phenoxy benzaldehyde and sodium cyanide single step reaction.The present invention compares with present existent method, has yield height, product purity height, cost is low, reaction conditions is gentle, operation is simple especially, reaction is easy to characteristics such as control, is more suitable in using in suitability for industrialized production.
The method that the present invention prepares fenvalerate comprises the steps:
1) add 2-(4-chloro-phenyl-)-3 Methylbutanoic acid and thionyl chloride and micro-N respectively in reactor, dinethylformamide or pyridine at room temperature stirred 3～4 hours, and suction filtration removes excessive thionyl chloride, got 2-(4-chloro-phenyl-)-3-methylbutyryl chlorine.
2) toluene solution with 2-(4-chloro-phenyl-)-3-methylbutyryl chlorine joins the triethylamine that fills 3-phenoxy benzaldehyde, sodium cyanide, water and organic solvent catalyst neutralisation amount, stir, after-30～80 ℃ of esterifications finish, separatory, boil off solvent, get fenvalerate.
In the above-mentioned reaction, the mol ratio of 2-(4-chloro-phenyl-)-3 Methylbutanoic acid and thionyl chloride is: 1: 1～1.2.Described organic solvent is aromatic hydrocarbons (as toluene, benzene, dimethylbenzene), hexanaphthene, normal hexane, Skellysolve A, normal heptane, sherwood oil or gasoline.
2-in the esterification (4-chloro-phenyl-)-3-methylbutyryl chlorine, 3-phenoxy benzaldehyde and sodium cyanide mole number such as can be pressed and add, or the excessive 5-30% of sodium cyanide.Temperature of reaction can be carried out in-30～80 ℃ of scopes, and reaction is spent the night, and best temperature of reaction is-15～40 ℃.
The present invention adopts triethylamine to make catalyzer, the directly synthetic fenvalerate of 2-(4-chloro-phenyl-)-3-methylbutyryl chlorine and 3-phenoxy benzaldehyde and sodium cyanide single step reaction.The present invention compares with present existent method, has yield height, product purity height, cost is low, reaction conditions is gentle, operation is simple especially, reaction is easy to characteristics such as control.Former medicine content of the present invention reaches more than 95%, and yield reaches more than 97%, is more suitable in using in suitability for industrialized production.
Embodiment
Embodiment 1
The preparation method of 2-(4-chloro-phenyl-)-3-methylbutyryl chlorine: in the round-bottomed flask that has induction stirring, add 0.47mol 2-(4-chloro-phenyl-)-3 Methylbutanoic acid and 0.52mol thionyl chloride and 2 N, dinethylformamide, under 20 ℃ temperature, stirred 4 hours, extract excessive thionyl chloride with water pump then.The gained acyl chlorides directly uses with toluene or hexanaphthene dissolving back.
The preparation method of fenvalerate: in three mouthfuls of reaction flasks, add 98.5%3-phenoxy benzaldehyde (24.73g), 97% sodium cyanide (6.06g), water and toluene add the triethylamine of catalytic amount to dissolving.Under the state that stirs, add the toluene solution of 2-(4-chloro-phenyl-)-3-methylbutyryl chlorine (0.104mmol).Reaction is spent the night under the room temperature, and after reaction finished, separatory boiled off solvent, got the former medicine of fenvalerate, and content is 96.0%, and yield is 99.1%.
Embodiment 2
In three mouthfuls of reaction flasks, add 98.5%3-phenoxy benzaldehyde (24.73g), 97% sodium cyanide (6.06g), the triethylamine of water and hexanaphthene and catalytic amount.Under the state that stirs, add the cyclohexane solution of 2-(4-chloro-phenyl-)-3-methylbutyryl chlorine (0.104mmol) (embodiment 1 preparation).Reaction is spent the night under the room temperature, and after reaction finished, separatory boiled off solvent, got the former medicine of fenvalerate, and content is 97.3%, and yield is 99.4%.
Claims (6)
1, a kind of preparation method of fenvalerate is characterized in that it comprises the steps:
1) add 2-(4-chloro-phenyl-)-3 Methylbutanoic acid and thionyl chloride and micro-N respectively in reactor, dinethylformamide or pyridine at room temperature stirred 3～4 hours, and suction filtration removes excessive thionyl chloride, got 2-(4-chloro-phenyl-)-3-methylbutyryl chlorine;
2) toluene solution with 2-(4-chloro-phenyl-)-3-methylbutyryl chlorine joins in the triethylamine that fills 3-phenoxy benzaldehyde, sodium cyanide, water and organic solvent and catalytic amount, stirs, and after-30～80 ℃ of reactions finished, separatory boiled off solvent, gets fenvalerate.
2,, it is characterized in that the mol ratio of described 2-(4-chloro-phenyl-)-3 Methylbutanoic acid and thionyl chloride is: 1: 1～1.2 according to the preparation method of the described fenvalerate of claim 1.
3,, it is characterized in that described organic solvent is toluene, benzene, dimethylbenzene, hexanaphthene, normal hexane, Skellysolve A, normal heptane, sherwood oil or gasoline according to the preparation method of the described fenvalerate of claim 1.
4,, it is characterized in that described organic solvent is toluene or hexanaphthene according to the preparation method of the described fenvalerate of claim 3.
5,, it is characterized in that 2-in the described esterification (4-chloro-phenyl-)-3-methylbutyryl chlorine, 3-phenoxy benzaldehyde and sodium cyanide mole ratio are according to the preparation method of the described fenvalerate of claim 1: 1: 1: 1, or the excessive 5-30% of sodium cyanide.
6,, it is characterized in that described esterification reaction temperature is-15～40 ℃ according to the preparation method of the described fenvalerate of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310106703 CN1239473C (en) | 2003-10-23 | 2003-10-23 | Fenvalerate preparing process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310106703 CN1239473C (en) | 2003-10-23 | 2003-10-23 | Fenvalerate preparing process |
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| CN1609099A CN1609099A (en) | 2005-04-27 |
| CN1239473C true CN1239473C (en) | 2006-02-01 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 200310106703 Expired - Fee Related CN1239473C (en) | 2003-10-23 | 2003-10-23 | Fenvalerate preparing process |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102675149A (en) * | 2012-04-23 | 2012-09-19 | 绩溪县庆丰天鹰生化有限公司 | Preparation method of fenvalerate |
| CN103159645B (en) * | 2013-03-26 | 2016-01-20 | 安徽海顺化工有限公司 | The alkylation reaction method of preparation 2-(4-chloro-phenyl-)-3-Methylbutanoyl chloride |
| CN103193621A (en) * | 2013-03-26 | 2013-07-10 | 安徽海顺化工有限公司 | Acylation reaction method for preparing 2-4-(chlorophenyl)-3-methylbutyryl chloride |
| CN106278944A (en) * | 2016-08-10 | 2017-01-04 | 江苏春江润田农化有限公司 | A kind of production method of fenvalerate |
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