CN101333194A - Method for preparing quizalofop-p-ethyl - Google Patents
Method for preparing quizalofop-p-ethyl Download PDFInfo
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- CN101333194A CN101333194A CNA2007101235023A CN200710123502A CN101333194A CN 101333194 A CN101333194 A CN 101333194A CN A2007101235023 A CNA2007101235023 A CN A2007101235023A CN 200710123502 A CN200710123502 A CN 200710123502A CN 101333194 A CN101333194 A CN 101333194A
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Abstract
The invention relates to a preparation method for quizalofop-p-ethyl, in particular to a method which uses p-hydroxybenzaldehyde to replace the raw material hydroquinone used in the traditional technology and react with S (-)-N-tosyl ethyl lactate to prepare R (+)-2-(p-oxy) propionate which is then reacted with 2,6- dichloro-quinoxaline to prepare high-purity quizalofop-p-ethyl through condensation.
Description
Technical field
What the present invention relates to is a kind of method for preparing the former medicine of weedicide quizalofopPethyl.
Background technology
QuizalofopPethyl is the dry land post-emergence herbicide, can prevent and kill off killing graminaceous weed in latifolious crop field such as soybean, peanut, cotton, potato, mung bean, watermelon, rape effectively.In the prior art, quizalofopPethyl is mainly used Resorcinol and 2, after the condensation of 6-dichloro-quinoxaline, makes with S (-)-p-toluenesulfonyl ethyl lactate reaction again.This technology mainly exists Resorcinol sewage difficult, and the not high shortcoming of the optical purity of quizalofopPethyl.
Summary of the invention
The objective of the invention is to seek a kind of method for preparing high-purity quizalofopPethyl, avoid producing the sewage that contains Resorcinol simultaneously.
Its main technical schemes is: p-Hydroxybenzaldehyde and S (-)-p-toluenesulfonyl ethyl lactate reaction are made R (+)-2-(to the aldehyde radical phenoxy group) ethyl propionate; carry out catalyzed oxidation again, hydrolysis gets R (+)-2-(para hydroxybenzene oxygen base) ethyl propionate; last with 2, the condensation of 6-dichloro-quinoxaline makes high-purity quizalofopPethyl.
This method can be represented with following reaction scheme:
Step (1):
Step (2):
Step (3):
Specific embodiments of the present invention comprises the steps:
(1) in solvent, adds p-Hydroxybenzaldehyde, S (-)-p-toluenesulfonyl ethyl lactate, mineral alkali, reflux to reacting completely, cold filtration, decompression steams solvent, add toluene and water and wash, get product R (+)-2-(to the aldehyde radical phenoxy group) ethyl propionate through underpressure distillation again;
(2) R (+)-2-(to the aldehyde radical phenoxy group) ethyl propionate is added to stirring and dissolving in the solvent, add dropping oxidizing agent behind the catalyzer again, finish, at a certain temperature stirring reaction, add then entry be hydrolyzed the back layering, the decompression precipitation get product R (+)-2-(para hydroxybenzene oxygen base) ethyl propionate;
(3) with 2, the 6-dichloro-quinoxaline is dissolved in the solvent, is added drop-wise to then in R (+)-2-(para hydroxybenzene oxygen base) the ethyl propionate solution that the alkali existence is arranged under the reflux conditions, drips and finishes, continue reaction to reacting completely, washing, precipitation, recrystallization get high-purity quizalofopPethyl product.
When carrying out wooden inventive method step (1), the mol ratio of p-Hydroxybenzaldehyde and S (-)-p-toluenesulfonyl ethyl lactate is 1: 1～2, preferred 1: 1～1.5.
Solvent described in the step (1) is DMF, benzene, toluene or acetonitrile.
Mineral alkali described in the step (1) is yellow soda ash or salt of wormwood, preferred salt of wormwood.
The mol ratio of (to the aldehyde radical phenoxy group) ethyl propionate of R (+)-2-described in the step (2) and oxygenant is 1: 1～2, preferred 1: 1.3～1.6.
Solvent described in the step (2) is benzene,toluene,xylene or chlorobenzene, is preferably benzene, toluene.
Oxygenant described in the step (2) is peroxy acid or hydrogen peroxide.Peroxy acid is Peracetic Acid or Perpropionic Acid, is preferably Peracetic Acid.
Catalyzer described in the step (2) is phospho-molybdic acid, phospho-wolframic acid or silicotungstic acid and similar heteropolyacid;
Temperature of reaction described in the step (2) is 20 ℃～80 ℃, preferred 40 ℃～60 ℃.
R (+)-2-described in the step (3) (para hydroxybenzene oxygen base) ethyl propionate and 2, the mol ratio of 6-dichloro-quinoxaline is 1～2: 1, preferred 1.1～1.6: 1.
The described solvent of step (3) is benzene or toluene.
The described alkali of step (3) is carbonate, sodium hydroxide or potassium hydroxide, is preferably sodium hydroxide.
Adopt preparation method provided by the invention for traditional method, its advantage is: (1) uses p-Hydroxybenzaldehyde to replace Resorcinol, has avoided containing the generation of Resorcinol sewage, contains the unmanageable environmental protection pressure of Resorcinol sewage thereby alleviated; (2) products obtained therefrom has higher optical purity, can reach 99.9%, thereby has improved the quality of product.
Embodiment
The present invention describes with following indefiniteness embodiment.
Embodiment 1
The preparation of R (+)-2-(to the aldehyde radical phenoxy group) ethyl propionate
In the flask that thermometer, condenser, agitator are housed; add the 100ml acetonitrile; add 12.2g (0.1mol) p-Hydroxybenzaldehyde then; 40.8g (0.15mol) S (-)-p-toluenesulfonyl ethyl lactate; the 25g Anhydrous potassium carbonate; be warming up to back flow reaction 5h under the stirring state, be cooled to room temperature, after the filtration; filtrate decompression steams acetonitrile; add toluene and water, tell organic layer, again through underpressure distillation; collect 130～140 ℃/1mmHg cut; get product 21.5g, content 98.3%, yield 95.2% (in p-Hydroxybenzaldehyde).
Embodiment 2
The preparation of R (+)-2-(para hydroxybenzene oxygen base) ethyl propionate
In the flask that thermometer, condenser, agitator are housed, add 80ml toluene, add 22.2g (0.1mol) R (+)-2-(to the aldehyde radical phenoxy group) ethyl propionate then, 0.5g phospho-molybdic acid, Dropwise 35 % Peracetic Acid 32.5g finishes under the stirring at room, slowly be warming up to 50 ℃ of stirring reaction 2h, after adding 5g water stirring 1h, be cooled to room temperature, add the washing of 30g water, layering, underpressure distillation steams toluene and gets product 21g, content 93.8%, yield 94.3%.
Embodiment 3
The preparation of R (+)-2-(para hydroxybenzene oxygen base) ethyl propionate
Operation is with example 2, and hydrogen peroxide replaces Peracetic Acid, content 93.2%, yield 92.6%.
Embodiment 4
The preparation of quizalofopPethyl
In the flask that thermometer, condenser, agitator are housed, add 50ml toluene, 19.9g (0.1mol) 2, the 6-dichloro-quinoxaline, 10g sodium hydroxide stirs and is warming up to backflow, slowly drips the toluene solution of 29.4g (0.14mol) R (+)-2-(para hydroxybenzene oxygen base) ethyl propionate then, drip and finish, continue insulation reaction to reacting completely, washing, precipitation, recrystallization get quizalofopPethyl product 36.4g, content 97.5%, ee 〉=99.9%, yield 95.1%.
Claims (7)
1, a kind of method for preparing high-purity quizalofopPethyl is characterized in that it comprises following steps:
(1) p-Hydroxybenzaldehyde and S (-)-p-toluenesulfonyl ethyl lactate reaction are made R (+)-2-(to the aldehyde radical phenoxy group) ethyl propionate.
(2) under the condition that solvent exists, with the product of (1) carry out catalyzed oxidation, hydrolysis gets R (+)-2-(para hydroxybenzene oxygen base) ethyl propionate.
(3) under the condition that solvent exists, use alkali to make acid binding agent, with the product and 2 of (2), the condensation of 6-dichloro-quinoxaline makes high-purity quizalofopPethyl.
2, according to the method for claim 1, it is characterized in that the described solvent of step (1) is DMF, benzene, toluene or acetonitrile, acid binding agent is yellow soda ash or salt of wormwood.
3,, it is characterized in that the amount of substance ratio of described p-Hydroxybenzaldehyde of step (1) and S (-)-p-toluenesulfonyl ethyl lactate is 1: 1～2 according to the method for claim 1.
4, according to the method for claim 1, it is characterized in that the described solvent of step (2) is benzene,toluene,xylene or chlorobenzene, the oxygenant that uses is peroxy acid or hydrogen peroxide.
5,, it is characterized in that the described catalyzer of step (2) is phospho-molybdic acid, phospho-wolframic acid or silicotungstic acid and similar heteropolyacid according to the method for claim 1.
6, according to the method for claim 1, it is characterized in that the described solvent of step (3) is benzene or toluene, used alkali is carbonate, sodium hydroxide or potassium hydroxide.
7, according to the method for claim 1, it is characterized in that step (3) is described 2, the amount of substance of 6-dichloro-quinoxaline and R (+)-2-(para hydroxybenzene oxygen base) ethyl propionate is 1: 1～2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007101235023A CN101333194A (en) | 2007-06-29 | 2007-06-29 | Method for preparing quizalofop-p-ethyl |
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2007101235023A CN101333194A (en) | 2007-06-29 | 2007-06-29 | Method for preparing quizalofop-p-ethyl |
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| CN101333194A true CN101333194A (en) | 2008-12-31 |
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| CNA2007101235023A Pending CN101333194A (en) | 2007-06-29 | 2007-06-29 | Method for preparing quizalofop-p-ethyl |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102010378A (en) * | 2010-12-27 | 2011-04-13 | 安徽丰乐农化有限责任公司 | Preparation method of quizalofop-p-ethyl |
| CN102250023A (en) * | 2011-08-08 | 2011-11-23 | 山东京博控股股份有限公司 | High yield synthetic method for quizalofop-p-ethyl |
| CN102590415A (en) * | 2012-01-19 | 2012-07-18 | 江苏丰山集团有限公司 | Method for determining content of sulfur impurities in intermediate 2,6-dichloro quinoxaline of quizalofop-p-ethyl technical material |
| CN107739343A (en) * | 2017-09-07 | 2018-02-27 | 京博农化科技股份有限公司 | A kind of environment-friendly type technique for producing Quizalotop-ethyl |
| CN107915686A (en) * | 2017-09-07 | 2018-04-17 | 京博农化科技股份有限公司 | A kind of Quizalotop-ethyl and its intermediate 4（6 chlorine, 2 quinoxaline epoxide）The synthetic method of phenol |
| CN112812002A (en) * | 2020-12-30 | 2021-05-18 | 锦州三丰科技有限公司 | Preparation method of (R) - (+) -2- (4-hydroxyphenoxy) propionic acid |
| CN115536518A (en) * | 2022-11-30 | 2022-12-30 | 苏州开元民生科技股份有限公司 | Preparation method of R- (+) -2- (4-hydroxyphenoxy) propionic acid |
-
2007
- 2007-06-29 CN CNA2007101235023A patent/CN101333194A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102010378A (en) * | 2010-12-27 | 2011-04-13 | 安徽丰乐农化有限责任公司 | Preparation method of quizalofop-p-ethyl |
| CN102250023A (en) * | 2011-08-08 | 2011-11-23 | 山东京博控股股份有限公司 | High yield synthetic method for quizalofop-p-ethyl |
| CN102590415A (en) * | 2012-01-19 | 2012-07-18 | 江苏丰山集团有限公司 | Method for determining content of sulfur impurities in intermediate 2,6-dichloro quinoxaline of quizalofop-p-ethyl technical material |
| CN107739343A (en) * | 2017-09-07 | 2018-02-27 | 京博农化科技股份有限公司 | A kind of environment-friendly type technique for producing Quizalotop-ethyl |
| CN107915686A (en) * | 2017-09-07 | 2018-04-17 | 京博农化科技股份有限公司 | A kind of Quizalotop-ethyl and its intermediate 4（6 chlorine, 2 quinoxaline epoxide）The synthetic method of phenol |
| CN107739343B (en) * | 2017-09-07 | 2020-06-19 | 京博农化科技股份有限公司 | Environment-friendly process for producing quizalofop-p-ethyl |
| CN112812002A (en) * | 2020-12-30 | 2021-05-18 | 锦州三丰科技有限公司 | Preparation method of (R) - (+) -2- (4-hydroxyphenoxy) propionic acid |
| CN115536518A (en) * | 2022-11-30 | 2022-12-30 | 苏州开元民生科技股份有限公司 | Preparation method of R- (+) -2- (4-hydroxyphenoxy) propionic acid |
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Open date: 20081231 |