CN109111373A - A kind of preparation method of Cyhalothrin - Google Patents
A kind of preparation method of Cyhalothrin Download PDFInfo
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- CN109111373A CN109111373A CN201811173449.2A CN201811173449A CN109111373A CN 109111373 A CN109111373 A CN 109111373A CN 201811173449 A CN201811173449 A CN 201811173449A CN 109111373 A CN109111373 A CN 109111373A
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- cyhalothrin
- preparation
- chlorine
- solvent
- trifluoro
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
Abstract
The present invention relates to a kind of preparation methods of Cyhalothrin, it is reacted using lanbda-cyhalothric acid with phosphorus trichloride, RS- cyanalcohol and Cyhalothrin is made, the reaction step includes: that lanbda-cyhalothric acid reacts three cyfluthrin chrysanthemum acyl chlorides of generation with phosphorus trichloride, three cyfluthrin chrysanthemum acyl chlorides reacted again with cyanalcohol be made Cyhalothrin, it is purified after Cyhalothrin under acetic acid solvent high temperature reflux carry out epimerism obtain cis- Cyhalothrin.The present invention has the advantages that method of the invention prepare Cyhalothrin purity is high, impurity content is few, molar yield is high, most importantly pharmacological property improve 1.8-2.2 times, achieve good economic benefit；Preparation method is safe and environment-friendly, is suitable for industrial production, is with a wide range of applications.
Description
Technical field
The present invention relates to chemical field, in particular to a kind of preparation method of Cyhalothrin.
Background technique
Gamma cyhalothrin is called trifluoro lambda-cyhalothrin, cyhalothrin, and insecticidal spectrum is wide, and activity is higher, and drug effect is fast
Speed, resistance of rainwater washing against after sprinkling, due to being cis- in the Cyhalothrin of prior art preparation and trans- trifluoro chlorine fluorine cyanogen chrysanthemum
The mixture of ester, after epimerism separates trans- trifluoro lambda-cyhalothrin, ultra high efficiency cyfloxylate insecticidal activity is
1.97~2.19 times of cyhalothrin, thus it has broad application prospects and good development space.
Through retrieving, 101723856 B of patent CN discloses a kind of method for preparing Cyhalothrin, has following step
It is rapid: 1. prepare mixed solution: by 3-Phenoxy-benzaldehyde, sodium cyanide solution, organic solvent and as the aminopyridine of catalyst or its spread out
Biology is mixed to get mixed solution；2. preparing the crude product containing Cyhalothrin: 0 DEG C~40 DEG C at a temperature of, to step
1. obtained mixed solution and dripping trifluoro chlorine cyanato- chlorine, stirs after dripping off, obtains the crude product containing Cyhalothrin；3. essence
System: the 2. crude product containing Cyhalothrin that step is obtained is layered, and oil reservoir is washed with water, and removing organic solvent obtains trifluoro chlorine
Cyano chrysanthemate crude oil；The available high-purity of the method for the invention, excellent color, high yield Cyhalothrin crude oil, and point
From simple, do not need to recrystallize, avoid the generation of waste mother liquor, reduce production cost；But there are still certain disadvantages:
The Cyhalothrin being prepared by the inventive method, drug effect are relatively low.
Therefore, a kind of three cyfluthrins that can be greatly improved Cyhalothrin pharmacological property and guarantee final products yield are researched and developed
The preparation method of pyrethroids is necessary.
Summary of the invention
Cyhalothrin pharmacological property can be greatly improved the technical problem to be solved in the present invention is to provide one kind and is guaranteed most
The preparation method of the Cyhalothrin of finished product yield.
In order to solve the above technical problems, the technical solution of the present invention is as follows: a kind of preparation method of Cyhalothrin, wound
New point is: the preparation method, which is reacted using trifluoro chlorine cyanic acid with phosphorus trichloride, cyanalcohol, is made Cyhalothrin, using
The product of transconfiguration is converted to cis- Cyhalothrin by epimerism；The preparation method specifically includes following step
It is rapid:
S1, the lanbda-cyhalothric acid that solvent and 10 times of quantity of solvent are added in round-bottomed flask, are then turned on stirring, and control in 30-
Phosphorus trichloride is added dropwise in 40min；
After S2, material add, 50-55 DEG C of reaction 3-5h is warming up to after 20-25 DEG C of stirring 8-9h again, after reaction, is taken off
It is molten to obtain trifluoro chlorine cyanato- chlorine；
S3, the trifluoro chlorine cyanato- chlorine for being mixed with solvent is added dropwise into cyanalcohol, process control temp is added dropwise and is no more than 40 DEG C, feed intake end
Afterwards, it is to slowly warm up to 55-60 DEG C, stirring 6-8h obtains Cyhalothrin crude product；
S4, Cyhalothrin crude product stood, be layered, oil reservoir is washed with water after continue to be layered, oil reservoir decompression precipitation obtains
Cyhalothrin；
S5,118-120 DEG C will be warming up to by addition acetic acid in Cyhalothrin, decompression boils off acetic acid after back flow reaction 6-8h, obtains
To Cyhalothrin.
Reaction principle:
Further, the solvent in the S1 is n,N-Dimethylformamide.
Further, the weight ratio of the phosphorus trichloride in the S1 and lanbda-cyhalothric acid is 1:5.
Further, the solvent in the S3 is toluene.
Further, the molar ratio of cyanalcohol and Cyhalothrin is 1:1 in the S3.
Further, the dosage of acetic acid is 1.2 times of Cyhalothrin in the S5.
The present invention has the advantages that the Cyhalothrin generated is reacted with cyanalcohol using traditional trifluoro chlorine cyanato- chlorine
It is cis- and trans- trifluoro lambda-cyhalothrin mixture, the method is using high temperature reflux in acid condition, so that trans- three
Fluorine lambda-cyhalothrin is fully converted to cis- trifluoro lambda-cyhalothrin, and 1.8-2.2 times, and final products yield can be improved in drug effect
Reach >=87.0%, and then the Cyhalothrin product purity prepared through the invention is high, impurity content is few, molar yield is high,
Good economic benefit is achieved, and preparation method of the invention is safe and environment-friendly, is suitable for industrial production.
Specific embodiment
The following examples can make professional and technical personnel that the present invention be more fully understood, but therefore not send out this
It is bright to be limited among the embodiment described range.
Embodiment
Present embodiment discloses a kind of preparation method of cis- Cyhalothrin, the preparation method uses acid flux material
The mode of high temperature reflux, specific step is as follows for the preparation method:
Embodiment 1
250g lanbda-cyhalothric acid is added in 500ml round-bottomed flask, continuously adds 25mL solvent N, N- dimethyl after opening stirring
50g phosphorus trichloride is slowly added dropwise in formamide, and control time for adding is 0.5h, after material adds, delays again after 25 DEG C of reaction 8h
Slowly 50 DEG C of reaction 3h are warming up to, precipitation obtains trifluoro chlorine cyanato- chlorine after fully reacting.
Cyanalcohol is added into reaction flask, control temperature of reaction system is 0-40 DEG C, and the trifluoro chlorine for being mixed with toluene solvant is added dropwise
Cyanato- chlorine after being added dropwise, is to slowly warm up to 55 DEG C, stirs 6h, obtain Cyhalothrin crude product.Then crude product is stood and is divided
Layer, after oil reservoir is washed three times, removing finish solvent obtains the Cyhalothrin of cis and trans mixing.
The mixture Cyhalothrin of 200g is added into 500mL reaction flask, adds the glacial acetic acid of 240g, slowly rises
To 118 DEG C, back flow reaction 6h, cooling, negative pressure is evaporated off acetic acid and obtains cis- Cyhalothrin temperature.
Embodiment 2
250g lanbda-cyhalothric acid is added in 500ml round-bottomed flask, continuously adds 25mL solvent N, N- dimethyl after opening stirring
50g phosphorus trichloride is slowly added dropwise in formamide, and control time for adding is 40min, after material adds, after 28 DEG C of reaction 8h again
50 DEG C of reaction 3h are to slowly warm up to, precipitation obtains trifluoro chlorine cyanato- chlorine after fully reacting.
Cyanalcohol is added into reaction flask, control temperature of reaction system is 0-40 DEG C, and the trifluoro chlorine for being mixed with toluene solvant is added dropwise
Cyanato- chlorine after being added dropwise, is to slowly warm up to 60 DEG C, stirs 6h, obtain Cyhalothrin crude product.Then crude product is stood and is divided
Layer, after oil reservoir is washed three times, removing finish solvent obtains the Cyhalothrin of cis and trans mixing.
The mixture Cyhalothrin of 200g is added into 500mL reaction flask, adds the glacial acetic acid of 240g, slowly rises
To 118 DEG C, back flow reaction 8h, cooling, negative pressure is evaporated off acetic acid and obtains cis- Cyhalothrin temperature.
Embodiment 3
250g lanbda-cyhalothric acid is added in 500ml round-bottomed flask, continuously adds 25mL solvent N, N- dimethyl after opening stirring
50g phosphorus trichloride is slowly added dropwise in formamide, and control time for adding is 35min, after material adds, after 28 DEG C of reaction 8h again
50 DEG C of reaction 3h are to slowly warm up to, precipitation obtains trifluoro chlorine cyanato- chlorine after fully reacting.
Cyanalcohol is added into reaction flask, control temperature of reaction system is 0-40 DEG C, and the trifluoro chlorine for being mixed with toluene solvant is added dropwise
Cyanato- chlorine after being added dropwise, is to slowly warm up to 55 DEG C, stirs 6h, obtain Cyhalothrin crude product.Then crude product is stood and is divided
Layer, after oil reservoir is washed three times, removing finish solvent obtains the Cyhalothrin of cis and trans mixing.
The mixture Cyhalothrin of 200g is added into 500mL reaction flask, adds the glacial acetic acid of 240g, slowly rises
To 118 DEG C, back flow reaction 6h, cooling, negative pressure is evaporated off acetic acid and obtains cis- Cyhalothrin temperature.
It is 98.2% that Cyhalothrin, which obtains content through liquid-phase chromatographic analysis, in embodiment 1-3, and Cyhalothrin rubs
Your yield is 87.1%, and drug effect is 1.8-2.2 times for generally mixing with body Cyhalothrin.
Basic principles and main features and advantages of the present invention of the invention have been shown and described above.The skill of the industry
Art personnel it should be appreciated that the present invention is not limited to the above embodiments, the above embodiments and description only describe
The principle of the present invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these
Changes and improvements all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and
Its equivalent thereof.
Claims (6)
1. a kind of preparation method of Cyhalothrin, it is characterised in that: the preparation method uses trifluoro chlorine cyanic acid and trichlorine
Change phosphorus, the obtained Cyhalothrin of cyanalcohol reaction, the product of transconfiguration is converted to cis- trifluoro using epimerism
Cypermethrin；The preparation method specifically comprises the following steps:
S1, the lanbda-cyhalothric acid that solvent and 10 times of quantity of solvent are added in round-bottomed flask, are then turned on stirring, and control in 30-
Phosphorus trichloride is added dropwise in 40min；
After S2, material add, 50-55 DEG C of reaction 3-5h is warming up to after 20-25 DEG C of stirring 8-9h again, after reaction, is taken off
It is molten to obtain trifluoro chlorine cyanato- chlorine；
S3, the trifluoro chlorine cyanato- chlorine for being mixed with solvent is added dropwise into cyanalcohol, process control temp is added dropwise and is no more than 40 DEG C, feed intake end
Afterwards, it is to slowly warm up to 55-60 DEG C, stirring 6-8h obtains Cyhalothrin crude product；
S4, Cyhalothrin crude product stood, be layered, oil reservoir is washed with water after continue to be layered, oil reservoir decompression precipitation obtains
Cyhalothrin；
S5,118-120 DEG C will be warming up to by addition acetic acid in Cyhalothrin, decompression boils off acetic acid after back flow reaction 6-8h, obtains
To Cyhalothrin.
2. the preparation method of Cyhalothrin according to claim 1, it is characterised in that: the solvent in the S1 is N,
Dinethylformamide.
3. the preparation method of Cyhalothrin according to claim 1, it is characterised in that: the phosphorus trichloride in the S1
Weight ratio with lanbda-cyhalothric acid is 1:5.
4. the preparation method of Cyhalothrin according to claim 1, it is characterised in that: the solvent in the S3 is first
Benzene.
5. the preparation method of Cyhalothrin according to claim 1, it is characterised in that: cyanalcohol and trifluoro in the S3
The molar ratio of cypermethrin is 1:1.
6. the preparation method of Cyhalothrin according to claim 1, it is characterised in that: the dosage of acetic acid in the S5
It is 1.2 times of Cyhalothrin.
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| CN201811173449.2A CN109111373A (en) | 2018-10-09 | 2018-10-09 | A kind of preparation method of Cyhalothrin |
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