CN110003051A - A kind of preparation method of cyhalofop-butyl standard items - Google Patents
A kind of preparation method of cyhalofop-butyl standard items Download PDFInfo
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- CN110003051A CN110003051A CN201910369511.3A CN201910369511A CN110003051A CN 110003051 A CN110003051 A CN 110003051A CN 201910369511 A CN201910369511 A CN 201910369511A CN 110003051 A CN110003051 A CN 110003051A
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- cyhalofop
- butyl
- cyano
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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
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Abstract
The invention discloses a kind of preparation methods of cyhalofop-butyl standard items.Using (R) -2- [4- (4- cyano -2- fluorophenoxy) phenoxy group] propionic acid and n-butanol as raw material, using acetonitrile as solvent, air-distillation is reacted under the effect of the catalyst, adds fresh acetonitrile in distillation.After the reaction was completed, recycling design, heating make cyhalofop-butyl at liquid, and washing removes catalyst, obtain cyhalofop-butyl standard items by recrystallization again after then removing moisture.Method of the invention is easy to operate, and gained standard items content is greater than 99%, can be applied in cyhalofop-butyl research and production.
Description
Technical field
The present invention relates to a kind of preparation methods of cyhalofop-butyl standard items, belong to technical field of pesticide.
Background technique
Cyhalofop-butyl is that The Dow Agrosciences, LLC. (Dow AgroSciences Company) opened first in 1987
A kind of paddy field herbicides special sent out and introduced to the market in 1992 is unique right in fragrant benzene oxycarboxylic acid ester herbicide
Rice has tight security and environment amenable New Herbicides, chemical name: (R) -2- [4- (4- cyano -2- fluorobenzene
Oxygroup) phenoxy group] butyl propionate.
Cyhalofop-butyl is the outer systemic herbicides of interior suction, is absorbed by the blade and leaf sheath of plant, bast conduction, and rapidly
It is degraded to cyanogen fluorine oxalic acid (ACID), accumulation inhibits acetyl coenzyme A carboxylase, make fat in the meristem zone of plant
Acid synthesis stops, and the growth division of cell cannot proceed normally, and the structure containing rouge such as membranous system is destroyed, and Plant death is finally resulted in.
But cyanogen fluorine oxalic acid, which is necessary for (R)-isomers, to be accumulated well in plant separate living tissue, play its clean property, otherwise inactivate.
Therefore, it is most important to play it activity for the optical activity of cyhalofop-butyl.
Need to use cyhalofop-butyl standard items in the research and production process of cyhalofop-butyl.The preparation of cyhalofop-butyl standard items
Cyhalofop-butyl crude product is usually first synthesized, is then purified using column chromatography, preparation the methods of chromatography or recrystallization.Synthesize cyanogen
During fluorine grass ester, side reactions, generated by-product and the cyhalofop-butyls such as a small amount of hydrolysis or alcoholysis occur for the cyano on raw material
With similar precursor structure, cause to be difficult to isolate and purify, the cyanogen fluorine obtained by usual manners such as silica gel column chromatography, recrystallizations
Careless ester standard items content 97~98%；It can get the cyhalofop-butyl standard items that content is greater than 98% by high pressure preparative liquid chromatography,
But high pressure preparative liquid chromatography use cost is high, and preparation amount is mostly milligram grade.
At present both at home and abroad it is published about the method for preparing cyhalofop-butyl mainly include the following types:
Li Meifang etc. (CN102584627B) discloses one kind with (R) -2- (4- hydroxyphenoxy) propionic acid and 3,4- difluorobenzonilyile
For raw material, obtain intermediate (R) -2- (4- (2- fluorine-4-nitrile)-phenoxy group) propionic acid by condensation reaction, intermediate again with light
The chlorination reagents such as gas effect generate intermediate (R) -2- (4- (2- fluorine-4-nitrile)-phenoxy group) propionyl chloride, finally and n-butanol into
Row esterification obtains cyhalofop-butyl.
Luo Liangming etc. (synthesis of cyhalofop-butyl, pesticide research and application, 2007,11 (1), 23-25) proposes a kind of conjunction
It at the route of cyhalofop-butyl, uses (S)-methyl lactate for raw material, prepares (S)-to benzene sulfonyl chloride cream with reacting benzene sulfonyl chloride
Acid esters, then synthesis (R) -2- (4- hydroxyphenoxy) ethyl propionate is reacted with hydroquinone, it is reacted later with 3,4- difluorobenzonilyile,
Using hydrolysis, lactate synthesis cyhalofop-butyl.
Yao Sheng etc. (CN102181496B) discloses a kind of method of enzyme' s catalysis cyhalofop-butyl, with (R) -2- [4- (4-
Cyano -2- fluorophenoxy) phenoxy group] ethyl propionate is raw material, enzymatically transesterification synthesizes cyhalofop-butyl, needs in reaction process
Specific lipase or protease is added.
R.Garth Pews etc. (US4894085) discloses a kind of 2- [4- (4- cyano -2- fluorophenoxy) phenoxy group] third
The preparation method of acid butyl ester is made using 2- [4- (4- cyano -2- fluorophenoxy) phenoxy group] methyl propionate as raw material with chlorination reagent
With intermediate 2- (4- (2- fluorine-4-nitrile)-phenoxy group) propionyl chloride is generated, esterification finally is carried out with n-butanol and obtains 2-
[4- (4- cyano -2- fluorophenoxy) phenoxy group] butyl propionate.
During the above several method synthesizes thick cyhalofop-butyl, a small amount of pair can occur during the reaction for the cyano on raw material
Reaction, generated by-product have similar precursor structure with cyhalofop-butyl, and the cyhalofop-butyl using the synthesis of these methods is logical
Cross conventional method be further purified preparation standard items content it is undesirable.Therefore it is necessary to develop a kind of cyhalofop-butyl standard
The preparation method of product.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of cyhalofop-butyl standard items, it is characterised in that: with (R) -2- [4-
(4- cyano -2- fluorophenoxy) phenoxy group] propionic acid is raw material, reaction dissolvent is acetonitrile, and reaction is under the effect of the catalyst and just
Butanol reaction synthesizes thick cyhalofop-butyl, chemical equation are as follows:
Raw material (R) -2- [4- (4- cyano -2- fluorophenoxy) phenoxy group] propionic acid, the scientific research personnel of this field can be according to correlation
The method of document announcement synthesizes.
Catalyst of the present invention is p-methyl benzenesulfonic acid or methanesulfonic acid, and dosage is (R) -2- [4- (4- cyano -2- fluorobenzene oxygen
Base) phenoxy group] propionic acid mass percent 0.1%~10%；Acetonitrile is reaction dissolvent；Reactant n-butanol and raw material (R) -2-
The molar ratio of [4- (4- cyano -2- fluorophenoxy) phenoxy group] propionic acid is 1.2~3.0；Reaction condition is air-distillation reaction, side
It distills acetonitrile side and fresh acetonitrile is added dropwise, when (R) -2- [4- (4- cyano -2- fluorophenoxy) phenoxy group] propionic acid content is less than 0.2%
Shi Fanying is completed；After the reaction was completed, recycling design, heating make cyhalofop-butyl liquid, and washing removes catalyst, and removing moisture obtains
Cyhalofop-butyl crude product is obtained, ethyl alcohol, normal propyl alcohol, isopropanol or n-butanol equal solvent recrystallization is reused and obtains cyhalofop-butyl standard
Product.
The preparation method of cyhalofop-butyl standard items provided by the invention, compared with prior art, the head of the invention
Secondary proposition uses acetonitrile as the reaction dissolvent for preparing cyhalofop-butyl standard items, and acetonitrile mole is far longer than original in reaction system
Expect (R) -2- [4- (4- cyano -2- fluorophenoxy) phenoxy group] propionic acid mole, the side reaction that cyano is occurred in reaction process
Substantially all occurring on the cyano of acetonitrile, produced by-product structure and cyhalofop-butyl difference are larger, and it is more easily separated, contained by raw material
Cyano occur side reaction probability it is minimum.
Method of the invention is not easy to operate, high to equipment requirement, and preparation cost is low, and gained standard items content is greater than 99%,
Cyhalofop-butyl research be can be applied to production, there is practicability.
Specific embodiment
In order to further appreciate that the present invention, the present invention is done below with reference to embodiment and is further described in detail, but this
Invent the range that claimed range is not limited to embodiment expression.
Embodiment 1
50 mL acetonitriles, 13.50 g are added into 250 mL there-necked flasks for atmospheric distillation plant with dropping funel and thermometer
(R) -2- [4- (4- cyano -2- fluorophenoxy) phenoxy group] propionic acid, 3.98 g n-butanols, 1.35 g p-methyl benzenesulfonic acid have been added
Finish and be heated to flowing back, fresh acetonitrile is added dropwise in distillation, distillates speed and rate of addition is about the same, as (R) -2- [4-
(4- cyano -2- fluorophenoxy) phenoxy group] propionic acid content less than 0.2% when reaction complete, then removed under reduced pressure solvent keeps temperature
Interior residue is liquid condition, is washed with water and (removes catalyst with 10.00 g of water) every time, organic layer removed under reduced pressure remains water twice
Get thick cyhalofop-butyl, thick cyhalofop-butyl is recrystallized to give cyhalofop-butyl standard items, content 99.1% by normal propyl alcohol.
Embodiment 2
50 mL acetonitriles, 13.50 g are added into 250 mL there-necked flasks for atmospheric distillation plant with dropping funel and thermometer
(R) -2- [4- (4- cyano -2- fluorophenoxy) phenoxy group] propionic acid, 9.96 g n-butanols, 0.0135 g p-methyl benzenesulfonic acid are added
It finishes and is heated to flowing back, fresh acetonitrile is added dropwise in distillation, distillate speed and rate of addition is about the same, as (R) -2-
It reacts and completes when [4- (4- cyano -2- fluorophenoxy) phenoxy group] propionic acid content is less than 0.2%, then removed under reduced pressure solvent, keep
Residue is liquid condition in temperature, is washed with water and (removes catalyst, organic layer removed under reduced pressure residual with 10.00 g of water) every time twice
Moisture obtains thick cyhalofop-butyl, and thick cyhalofop-butyl obtains cyhalofop-butyl standard items, content 99.0% by ethyl alcohol recrystallization.
Embodiment 3
50 mL acetonitriles, 13.50 g are added into 250 mL there-necked flasks for atmospheric distillation plant with dropping funel and thermometer
(R) -2- [4- (4- cyano -2- fluorophenoxy) phenoxy group] propionic acid, 7.58 g n-butanols, 0.50 g p-methyl benzenesulfonic acid have been added
Finish and be heated to flowing back, fresh acetonitrile is added dropwise in distillation, distillates speed and rate of addition is about the same, as (R) -2- [4-
(4- cyano -2- fluorophenoxy) phenoxy group] propionic acid content less than 0.2% when reaction complete, then removed under reduced pressure solvent keeps temperature
Interior residue is liquid condition, is washed with water and (removes catalyst with 10.00 g of water) every time, organic layer removed under reduced pressure remains water twice
Get thick cyhalofop-butyl, thick cyhalofop-butyl is recrystallized to give cyhalofop-butyl standard items, content 99.1% by n-butanol.
Embodiment 4
50 mL acetonitriles, 13.50 g are added into 250 mL there-necked flasks for atmospheric distillation plant with dropping funel and thermometer
(R) -2- [4- (4- cyano -2- fluorophenoxy) phenoxy group] propionic acid, 7.58 g n-butanols, 1.35 g methanesulfonic acids, addition, which finishes, to be added
Fresh acetonitrile is added dropwise in distillation to flowing back in heat, distillates speed and rate of addition is about the same, when (R) -2- [4- (4- cyanogen
Base -2- fluorophenoxy) phenoxy group] propionic acid content less than 0.2% when reaction complete, then removed under reduced pressure solvent keeps residual in temperature
Object is liquid condition, is washed with water and (removes catalyst with 10.00 g of water) every time, organic layer removed under reduced pressure residual moisture obtains twice
Thick cyhalofop-butyl, thick cyhalofop-butyl obtain cyhalofop-butyl standard items, content 99.0% by recrystallisation from isopropanol.
Embodiment 5
100 mL acetonitriles, 13.50 g are added into 250 mL there-necked flasks for atmospheric distillation plant with dropping funel and thermometer
(R) -2- [4- (4- cyano -2- fluorophenoxy) phenoxy group] propionic acid, 6.20 g n-butanols, 0.50 g methanesulfonic acid, addition, which finishes, to be added
Fresh acetonitrile is added dropwise in distillation to flowing back in heat, distillates speed and rate of addition is about the same, when (R) -2- [4- (4- cyanogen
Base -2- fluorophenoxy) phenoxy group] propionic acid content less than 0.2% when reaction complete, then removed under reduced pressure solvent keeps residual in temperature
Object is liquid condition, is washed with water and (removes catalyst with 10.00 g of water) every time, organic layer removed under reduced pressure residual moisture obtains twice
Thick cyhalofop-butyl, thick cyhalofop-butyl are recrystallized to give cyhalofop-butyl standard items, content 99.4% by n-butanol.
Embodiment 6
100 mL acetonitriles, 13.50 g are added into 250 mL there-necked flasks for atmospheric distillation plant with dropping funel and thermometer
(R) -2- [4- (4- cyano -2- fluorophenoxy) phenoxy group] propionic acid, 6.20 g n-butanols, 0.50 g p-methyl benzenesulfonic acid have been added
Finish and be heated to flowing back, fresh acetonitrile is added dropwise in distillation, distillates speed and rate of addition is about the same, as (R) -2- [4-
(4- cyano -2- fluorophenoxy) phenoxy group] propionic acid content less than 0.2% when reaction complete, then removed under reduced pressure solvent, decompression is de-
Except solvent, keeping residue in temperature is liquid condition, is washed with water and (removes catalyst, organic layer with 10.00 g of water) every time twice
Removed under reduced pressure residual moisture obtains thick cyhalofop-butyl, and thick cyhalofop-butyl is recrystallized to give cyhalofop-butyl standard items by n-butanol,
Content 99.3%.
Claims (5)
1. a kind of preparation method of cyhalofop-butyl standard items, it is characterised in that: with (R) -2- [4- (4- cyano -2- fluorophenoxy)
Phenoxy group] propionic acid and n-butanol be raw material, using acetonitrile as reaction dissolvent, cyhalofop-butyl crude product is synthesized under the effect of the catalyst,
Then cyhalofop-butyl standard items are obtained by post-processing.
2. preparation method according to claim 1, it is characterised in that: the catalyst is p-methyl benzenesulfonic acid or methylsulphur
Acid, dosage are the 0.1%~10% of (R) -2- [4- (4- cyano -2- fluorophenoxy) phenoxy group] propionic acid mass percent.
3. preparation method according to claim 1, it is characterised in that: n-butanol and (R) -2- [4- (4- cyano -2- fluorobenzene
Oxygroup) phenoxy group] propionic acid molar ratio be 1.2~3.0.
4. preparation method according to claim 1, it is characterised in that: reaction condition is air-distillation reaction, in distillation
Fresh acetonitrile is added, when (R) -2- [4- (4- cyano -2- fluorophenoxy) phenoxy group] propionic acid content is less than 0.2%, has been reacted
At.
5. preparation method according to claim 1, it is characterised in that: it is described after the reaction was completed, recycling design, heating make cyanogen
For fluorine grass ester at liquid, washing removes catalyst, and removing moisture obtains cyhalofop-butyl crude product, reuses ethyl alcohol, normal propyl alcohol, isopropanol
Or n-butanol equal solvent recrystallization obtains cyhalofop-butyl standard items.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102584627A (en) * | 2012-02-15 | 2012-07-18 | 江苏快达农化股份有限公司 | Synthetic method of cyhalofop-butyl active compound |
| CN105566158A (en) * | 2016-02-02 | 2016-05-11 | 江苏丰山集团股份有限公司 | Method for preparing cyhalofop-butyl |
| CN105601538A (en) * | 2016-02-02 | 2016-05-25 | 江苏丰山集团股份有限公司 | Preparation method of cyhalofop-butyl |
| CN107628967A (en) * | 2017-08-23 | 2018-01-26 | 连云港世杰农化有限公司 | A kind of method for synthesizing cyhalofop-butyl |
| CN108378057A (en) * | 2018-03-27 | 2018-08-10 | 安徽圣丰生化有限公司 | A kind of rice weeding composition of Han metamifops |
| CN109651140A (en) * | 2018-12-12 | 2019-04-19 | 江苏中旗科技股份有限公司 | A kind of synthetic method of cyhalofop-butyl active compound |
-
2019
- 2019-05-06 CN CN201910369511.3A patent/CN110003051A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102584627A (en) * | 2012-02-15 | 2012-07-18 | 江苏快达农化股份有限公司 | Synthetic method of cyhalofop-butyl active compound |
| CN105566158A (en) * | 2016-02-02 | 2016-05-11 | 江苏丰山集团股份有限公司 | Method for preparing cyhalofop-butyl |
| CN105601538A (en) * | 2016-02-02 | 2016-05-25 | 江苏丰山集团股份有限公司 | Preparation method of cyhalofop-butyl |
| CN107628967A (en) * | 2017-08-23 | 2018-01-26 | 连云港世杰农化有限公司 | A kind of method for synthesizing cyhalofop-butyl |
| CN108378057A (en) * | 2018-03-27 | 2018-08-10 | 安徽圣丰生化有限公司 | A kind of rice weeding composition of Han metamifops |
| CN109651140A (en) * | 2018-12-12 | 2019-04-19 | 江苏中旗科技股份有限公司 | A kind of synthetic method of cyhalofop-butyl active compound |
Non-Patent Citations (2)
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| 张涛等: "氰氟草醋手性合成的生物催化剂筛选", 《20 12 年全国第18 届有机和精细化工中间体学术交流会论文集》 * |
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Application publication date: 20190712 |