CN103709113A - Synthetic method of herbicide safener isoxadifen-ethyl - Google Patents
Synthetic method of herbicide safener isoxadifen-ethyl Download PDFInfo
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- CN103709113A CN103709113A CN201310567560.0A CN201310567560A CN103709113A CN 103709113 A CN103709113 A CN 103709113A CN 201310567560 A CN201310567560 A CN 201310567560A CN 103709113 A CN103709113 A CN 103709113A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
- C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
- C07D261/04—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
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Abstract
The invention discloses a synthetic method of herbicide safener isoxadifen-ethyl, the isoxadifen-ethyl is prepared by reaction of 1, 1-diphenyl ethylene and ethyl 2-chloro-2-(hydroxyimino)acetate under the effects of an alkali metal compound. The synthetic method is mild in reaction, simple in operation, high in yield, low in pollution, and easy to industrial production.
Description
Technical field
The invention belongs to synthetic field, be specifically related to the synthetic method of a kind of effective herbicide-safener Shuan Ben oxazole acid.
Background technology
The acid of Shuan Ben oxazole, another name Shuan Ben oxazole acid-ethyl, chemical name 4,5-dihydro-5,5-phenylbenzene-1,2-azoles-3-carboxylic acid, ethyl ester, English name Isoxadifen-ethyl, English another name Ethyl4,5-dihydro-5,5-diphenylisoxazol-3-carboxylate, CAS NO.163520-33-0, molecular formula C18H17NO3, molecular weight 295.33.
The mechanism of action of herbicide-safener: herbicide-safener (Safener) is called again toxinicide and protective material, refers to the poisoning of avoiding weedicide for cover crop, thus the security of crop and the compound of improvement weed control efficacy increased.Herbicide-safener has the optionally ability that strengthens weedicide being applied between crops and weeds, it not only can improve the resistance of crop, the infringement that cover crop avoids pesticide residue, also can be by the problem of preventing and kill off that solves difficulty and cut weeds.Therefore its study on the synthesis is had great importance and market widely.In the Major Maize of Shuan Ben oxazole acid at present, be used as herbicide-safener.
Preparation for the acid of Shuan Ben oxazole, the isoxazole class herbicide-safener of Shi You Sanofi-Aventis research and development the earliest, the weeds that are mainly used to prevent and kill off a year between corn field and give birth to throughout the year etc., the synthetic route of present stage bis-Ben oxazole acid is less, is mainly to obtain by diphenylethlene and the addition reaction of chloro glyoxylic acid oxime ethyl ester initial ring.Existing preparation method has:
DE4331448 bibliographical information chloro glyoxylic acid oxime ethyl ester, diphenylethlene and acid binding agent triethylamine prepare Shuan Ben oxazole acid.But it is many that this synthetic method produces impurity, needs column chromatography for separation, yield 82%.The method is unfavorable for large-scale industrial production.
Document < < agricultural chemicals > > o. 11th the 51st volume in 2012, slowly drips diphenylethlene and acid binding agent triethylamine and prepares the acid of Shuan Ben oxazole with chloro glyoxylic acid oxime ethyl ester in cyclohexane solvent under room temperature.But this synthetic method is when cycloaddition generates product, and the by product with approximately 20% generates, and makes product yield lower, need column chromatography for separation, yield only has 64% (coming in diphenylethlene), and three wastes problem is difficult to greatly process, and is unfavorable for large-scale industrial production.
Summary of the invention
The object of the invention is existing Shuan Ben oxazole acid preparation technology to improve, solved when cycloaddition reaction with the generation of approximately 20% by product, greatly improved the yield of product, be beneficial to large-scale industrial production.
Object of the present invention can reach by following measures:
A synthetic method for herbicide-safener Shuan Ben oxazole acid, 1，1-diphenylethylene reacts under alkali metal compound effect with chloro glyoxylic acid oxime ethyl ester, the acid of preparation Shuan Ben oxazole, its reaction process is as follows:
In present method, the mol ratio of 1，1-diphenylethylene and chloro glyoxylic acid oxime ethyl ester is 1:1～3, preferably 1:1.5～2.5.
In the method, alkali metal compound is selected from alkaline carbonate, alkali metal hydrocarbonate or alkali metal hydroxide; Preferred sodium bicarbonate, saleratus or salt of wormwood.Suitable alkali metal compound is conducive to the carrying out of reaction.The mol ratio of 1，1-diphenylethylene and alkali metal compound is 1:2～6, preferably 1:4～5.
In the method, reaction solvent is selected from methylene dichloride, Virahol, methyl alcohol, epoxy six ring or sherwood oils; Preferred methylene dichloride, Virahol or methyl alcohol.The forward that suitable reaction solvent is conducive to reaction carries out.Chloro glyoxylic acid oxime ethyl ester is 1:2～1:5 with weight of solvent ratio.
In the method, temperature of reaction is 15～150 ℃, preferably 30～100 ℃, and further preferably 50～80 ℃, most preferably 60～70 ℃.The variation meeting of temperature of reaction produces considerable influence to the process of reaction.
In the method, the aftertreatment of reaction is: reaction solution is cooled to 10 ℃ of following rear acidifyings, separates out product, filter, be drying to obtain.
The present invention adopts the method treat different things alike to react, reaction temperature and, simple to operate, mild condition, yield is high, pollutes littlely, aftertreatment produces inorganic salt and is easy to process, and is conducive to large-scale industrial production.
Embodiment
Embodiment 1
When temperature is 20-25 ℃, in the reaction flask of 250 milliliters, add 1,30 grams of 1-diphenylethlenes (0.166 mole), 43.5 grams of chloro glyoxylic acid oxime ethyl esters (0.287 mole), 120 grams of Virahols, 58 grams of (0.69 mole) stir about 1-4 hour of sodium bicarbonate, material is slowly warming up to 60-70 ℃, stirs after 3-6 hour, be cooled to below 10 ℃, use dilute hydrochloric acid acidifying, separate out product, filter, wash filter cake with water, after oven dry, obtain product 46.7g, content 97.3%, yield 95%(is in 1，1-diphenylethylene).
Embodiment 2
When temperature is 20-25 ℃, in the reaction flask of 250 milliliters, add 1,30 grams of 1-diphenylethlenes (0.166 mole), 43.5 grams of chloro glyoxylic acid oxime ethyl esters (0.287 mole), 120 grams of Virahols, 69 grams of (0.69 mole) stir about 1-4 hour of saleratus, material is slowly warming up to 60-70 ℃, stirs after 3-6 hour, be cooled to below 10 ℃, use dilute hydrochloric acid acidifying, separate out product, filter, wash filter cake with water, after oven dry, obtain product 41.8g, content 95.5%, yield 85%(is in 1，1-diphenylethylene).
Embodiment 3
When temperature is 20-25 ℃, in the reaction flask of 2000 milliliters, add 1,30 grams of 1-diphenylethlenes (0.166 mole), 43.5 grams of chloro glyoxylic acid oxime ethyl esters (0.287 mole), 120 grams of Virahols, 95.3 grams of (0.69 mole) stir about 1-4 hour of salt of wormwood, material is slowly warming up to 60-70 ℃, stirs after 3-6 hour, be cooled to below 10 ℃, use dilute hydrochloric acid acidifying, separate out product, filter, wash filter cake with water, after oven dry, obtain product 44g, content 93.8%, yield 89.6%(is in 1，1-diphenylethylene).
Embodiment 4
When temperature is 20-25 ℃, in the reaction flask of 2000 milliliters, add 1,120 grams of 1-diphenylethlenes (0.664 mole), 240 grams of chloro glyoxylic acid oxime ethyl esters (1.584 moles), 1000 grams of Virahols, 240 grams of (2.857 moles) stir about 1-4 hour of sodium bicarbonate, material is slowly warming up to 60-70 ℃, stirs after 3-6 hour, be cooled to below 10 ℃, use dilute hydrochloric acid acidifying, separate out product, filter, wash filter cake with water, after oven dry, obtain product 188.7g, content 95.8%, yield 96%(is in 1，1-diphenylethylene).
Embodiment 5
When temperature is 20-25 ℃, in the reaction flask of 250 milliliters, add 1,30 grams of 1-diphenylethlenes (0.166 mole), 43.5 grams of chloro glyoxylic acid oxime ethyl esters (0.287 mole), 100 grams of methylene dichloride, 58.0 grams of (0.69 mole) stir about 1-4 hour of sodium bicarbonate, material is slowly warming up to 45-48 ℃ of backflow 3-6 hour, be cooled to below 10 ℃, use dilute hydrochloric acid acidifying, separate out product, filter, wash filter cake with water, after oven dry, obtain product 32g, content 82.0%, yield 65.2%(is in 1，1-diphenylethylene).
Embodiment 6
When temperature is 20-25 ℃, in the reaction flask of 250 milliliters, add 1,30 grams of 1-diphenylethlenes (0.166 mole), 43.5 grams of chloro glyoxylic acid oxime ethyl esters (0.287 mole), 100 grams of methyl alcohol, 58.0 grams of (0.69 mole) stir about 1-4 hour of sodium bicarbonate, material is slowly warming up to 65-70 ℃ of backflow 3-6 hour, be cooled to below 10 ℃, use dilute hydrochloric acid acidifying, separate out product, filter, wash filter cake with water, after oven dry, obtain product 28g, content 89.6%, yield 57%(is in 1，1-diphenylethylene).
Embodiment 7
When temperature is 20-25 ℃, in the reaction flask of 250 milliliters, add 1,30 grams of 1-diphenylethlenes (0.166 mole), 43.5 grams of chloro glyoxylic acid oxime ethyl esters (0.287 mole), 120 grams of Virahols, 27.6 grams of (0.69 mole) stir about 1-4 hour of sodium hydroxide, material is slowly warming up to 60-70 ℃, stirs after 3-6 hour, be cooled to below 10 ℃, use dilute hydrochloric acid acidifying, separate out product, filter, wash filter cake with water, after oven dry, obtain product 26.1, content 86.3%, yield 53.26%(is in 1，1-diphenylethylene).
Embodiment 8
When temperature is 20-25 ℃, in the reaction flask of 250 milliliters, add 1,30 grams of 1-diphenylethlenes (0.166 mole), 43.5 grams of chloro glyoxylic acid oxime ethyl esters (0.287 mole), 120 grams of Virahols, 38.6 grams of (0.69 mole) stir about 1-4 hour of potassium hydroxide, material is slowly warming up to 60-70 ℃, stirs after 3-6 hour, be cooled to below 10 ℃, use dilute hydrochloric acid acidifying, separate out product, filter, wash filter cake with water, after oven dry, obtain product 31.8g, content 89.3%, yield 64.71%(is in 1，1-diphenylethylene).
Claims (8)
1. a synthetic method for the two benzene oxazole acid of herbicide-safener, is characterized in that 1，1-diphenylethylene reacts under alkali metal compound effect with chloro glyoxylic acid oxime ethyl ester, the two benzene oxazole acid of preparation, and its reaction process is as follows:
2. synthetic method according to claim 1, is characterized in that the mol ratio of 1，1-diphenylethylene and chloro glyoxylic acid oxime ethyl ester is 1:1～3, preferably 1:1.5～2.5.
3. synthetic method according to claim 1, is characterized in that described alkali metal compound is selected from alkaline carbonate, alkali metal hydrocarbonate or alkali metal hydroxide; Preferred sodium bicarbonate, saleratus or salt of wormwood.
4. synthetic method according to claim 1, the mol ratio that it is characterized in that 1，1-diphenylethylene and alkali metal compound is 1:2～6, preferably 1:4～5.
5. synthetic method according to claim 1, is characterized in that the solvent of reaction is selected from methylene dichloride, Virahol, methyl alcohol, epoxy six ring or sherwood oils; Preferred methylene dichloride, Virahol or methyl alcohol.
6. synthetic method according to claim 1, is characterized in that chloro glyoxylic acid oxime ethyl ester and weight of solvent ratio are 1:2～1:5.
7. synthetic method according to claim 1, is characterized in that temperature of reaction is 15～150 ℃, preferably 30～100 ℃, and further preferably 50～80 ℃, most preferably 60～70 ℃.
8. synthetic method according to claim 1, is characterized in that after reaction, and reaction solution is cooled to 10 ℃ of following rear acidifyings, separates out product, filters, is drying to obtain.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107652245A (en) * | 2017-08-24 | 2018-02-02 | 郑州手性药物研究院有限公司 | Chiral isoxadifen ethyl ester compound and its preparation method and application |
| CN108440435A (en) * | 2018-03-21 | 2018-08-24 | 重庆化工职业学院 | A kind of synthetic method of the isoxadifen of suitable industrialized production |
| CN112979494A (en) * | 2021-02-02 | 2021-06-18 | 河南佰研生物科技有限公司 | Method for synthesizing bisbenzoxazole acid intermediate chlorooximido ethyl acetate |
| CN113024480A (en) * | 2021-03-03 | 2021-06-25 | 河南省农业科学院植物保护研究所 | 4, 5-dihydro-5, 5-diphenyl isoxazole-3-formamide compound and application thereof |
| CN113135866A (en) * | 2020-01-17 | 2021-07-20 | 河北谷之润科技有限公司 | Ethyl bisbenzoxazolate with few impurities and preparation method thereof |
| CN115806531A (en) * | 2021-09-14 | 2023-03-17 | 新发药业有限公司 | Preparation method of 4, 5-dihydro-5, 5-diphenyl isoxazole-3-formic acid and derivatives thereof |
| CN115806530A (en) * | 2021-09-14 | 2023-03-17 | 新发药业有限公司 | Preparation method of isoxadifen |
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| CN1133038A (en) * | 1993-09-16 | 1996-10-09 | 赫彻斯特-舍林农业发展有限公司 | Substituted isoxazolines, process for producing them, agents containing them and their use as safeners |
| CN103172582A (en) * | 2013-03-25 | 2013-06-26 | 江苏省农用激素工程技术研究中心有限公司 | Method for preparing isoxadifen |
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2013
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Patent Citations (2)
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| CN1133038A (en) * | 1993-09-16 | 1996-10-09 | 赫彻斯特-舍林农业发展有限公司 | Substituted isoxazolines, process for producing them, agents containing them and their use as safeners |
| CN103172582A (en) * | 2013-03-25 | 2013-06-26 | 江苏省农用激素工程技术研究中心有限公司 | Method for preparing isoxadifen |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107652245A (en) * | 2017-08-24 | 2018-02-02 | 郑州手性药物研究院有限公司 | Chiral isoxadifen ethyl ester compound and its preparation method and application |
| CN108440435A (en) * | 2018-03-21 | 2018-08-24 | 重庆化工职业学院 | A kind of synthetic method of the isoxadifen of suitable industrialized production |
| CN113135866A (en) * | 2020-01-17 | 2021-07-20 | 河北谷之润科技有限公司 | Ethyl bisbenzoxazolate with few impurities and preparation method thereof |
| CN112979494A (en) * | 2021-02-02 | 2021-06-18 | 河南佰研生物科技有限公司 | Method for synthesizing bisbenzoxazole acid intermediate chlorooximido ethyl acetate |
| CN113024480A (en) * | 2021-03-03 | 2021-06-25 | 河南省农业科学院植物保护研究所 | 4, 5-dihydro-5, 5-diphenyl isoxazole-3-formamide compound and application thereof |
| CN113024480B (en) * | 2021-03-03 | 2022-05-06 | 河南省农业科学院植物保护研究所 | 4, 5-dihydro-5, 5-diphenyl isoxazole-3-formamide compound and application thereof |
| CN115806531A (en) * | 2021-09-14 | 2023-03-17 | 新发药业有限公司 | Preparation method of 4, 5-dihydro-5, 5-diphenyl isoxazole-3-formic acid and derivatives thereof |
| CN115806530A (en) * | 2021-09-14 | 2023-03-17 | 新发药业有限公司 | Preparation method of isoxadifen |
| CN115806531B (en) * | 2021-09-14 | 2024-05-28 | 新发药业有限公司 | Preparation method of 4, 5-dihydro-5, 5-diphenyl isoxazole-3-formic acid and derivatives thereof |
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Address after: No. 309 Changfeng River Road, Nanjing Chemical Industrial Park, Liuhe District, Nanjing, Jiangsu Applicant after: Jiangsu Zhongqi Polytron Technologies Inc Address before: No. 309 Changfeng River Road, Nanjing Chemical Industrial Park, Liuhe District, Nanjing, Jiangsu Applicant before: Jiangsu Flag Chemical Industry Co., Ltd. |
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Application publication date: 20140409 |