CN104592103A - Method for synthesizing fluroxypyr ester - Google Patents
Method for synthesizing fluroxypyr ester Download PDFInfo
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- CN104592103A CN104592103A CN201510047181.8A CN201510047181A CN104592103A CN 104592103 A CN104592103 A CN 104592103A CN 201510047181 A CN201510047181 A CN 201510047181A CN 104592103 A CN104592103 A CN 104592103A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/72—Nitrogen atoms
- C07D213/73—Unsubstituted amino or imino radicals
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for synthesizing fluroxypyr ester. The method comprises the following steps: dissolving 4-amido-3,5-dichloro-2,6 difluoropyridine into a solvent; adding glycollate, an acid-binding agent and a catalyst, heating, and keeping temperature till condensation reaction is complete; and carrying out post-processing to obtain the fluroxypyr ester. The method disclosed by the invention has the beneficial effects of enabling the reaction to be well carried out in a non-polar solvent, namely methylbenzene and the like, by catalyzing the reaction through a phase transfer catalyst, being moderate in condition and wide in application condition, achieving the easiness and convenience for post-processing operation and being simple in route and reduced in cost compared with the traditional process for synthesizing a fluroxypyr ester intermediate.
Description
Technical field
The present invention relates to technical field of fine, specifically relate to a kind of synthetic method of fluroxypyr ester.
Background technology
Fluroxypyr ester comprises fluroxypyr secondary monooctyl ester, fluroxypyr methyl esters, fluroxypyr ethyl ester etc., and fluroxypyr methyl esters, fluroxypyr ethyl ester etc. prepare agricultural chemicals: the important intermediate of fluroxypyr acid and the secondary monooctyl ester of fluroxypyr.And the secondary monooctyl ester of fluroxypyr (1-methylheptyl (4-amino-3, the fluoro-2-pyridyloxy of the chloro-6-of 5-bis-) acetic ester) be the organic heterocyclic class weedicide that LG-DOW Yi Nong Chemical Co., Ltd. develops, a kind of fluorine-containing efficient, low toxicity, low residue weedicide, have at stubble and succession crop high safety, working life is wide, consumption is few, the feature that miscibility is good, always deeply by the favor of user.
The preparation method of fluroxypyr ester has carried out some researchs abroad, mainly by 4-amino-3,5-bis-chloro-2,6-difluoro pyridine pyridine synthesis phenol sodium, then react the obtained fluroxypyr monooctyl ester second month in a season with Mono Chloro Acetic Acid secondary monooctyl ester, or with the Reactive Synthesis such as methyl chloroacetate, ethyl chloroacetate fluroxypyr lower member ester, then the secondary monooctyl ester of fluroxypyr is obtained through transesterification reaction, current method can obtain good reaction yield, but the method route is longer, and still has problems in separation, drying, environmental protection etc.
Summary of the invention
For prior art Problems existing, the invention provides a kind of route simple, the method for easy to operate synthesis fluroxypyr ester ((the fluoro-2-pyridine of amino-3, the 5-bis-chloro-6-of 4-) oxygen base)-acetic ester; The present invention adopts catalyst, by 4-amino-3, chloro-2, the 6-difluoro pyridines of 5-bis-and glycolic acid esters react, and directly can obtain the secondary monooctyl ester of fluroxypyr, or the intermediate such as fluroxypyr methyl esters and ethyl ester, decrease reactions steps, this reaction simultaneously can be carried out in the non-polar solvents such as toluene, mild condition, simplify post-processing operation, reduce cost.Concrete technical scheme is as follows.
The method of the synthesis fluroxypyr ester that the application provides, comprise: add 4-amino-3 in a solvent, 5-bis-chloro-2,6-difluoro pyridine and acid binding agent, be heated to 60-150 DEG C, drip ethyl glycolate, reaction is after 8-15h completes to condensation reaction, and through adding water, thermally stratified layer, the treatment step such as drying obtain fluroxypyr ester.
The structural formula of wherein said fluroxypyr ester is as follows:
r:1-8 alkyl;
The structure of described ethyl glycolate is as follows:
r:1-8 alkyl;
Described 4-amino-3,5-bis-chloro-2, the structural formula of 6 difluoro pyridines is as follows:
；
Described reaction process is as follows:
r:1-8 alkyl.
Preferably, in the synthetic method of fluroxypyr ester of the present invention, also comprise catalyzer, described catalyzer is selected from least one in tetrabutylammonium iodide, tetraethyl ammonium iodide, 4 bromide, Tetrabutyl amonium bromide, tetrabutylammonium chloride, benzyl triethyl ammonium bromide, Tetraphenylphosphonium Bromide, especially, when solvent selects toluene, hexanaphthene, use catalyst effect more obviously good.
Preferably, in the synthetic method of fluroxypyr ester of the present invention, the mol ratio of described catalyzer and amino-3,5-bis-chloro-2, the 6-difluoro pyridines of 4-is 0.01-0.1:1.
Preferably, in the synthetic method of fluroxypyr ester of the present invention, the mol ratio of described ethyl glycolate and amino-3,5-bis-chloro-2, the 6-difluoro pyridines of 4-is 1.05-1.5:1.
Preferably, in the synthetic method of fluroxypyr ester of the present invention, described acid binding agent, selects and common are machine alkali or mineral alkali, reduce raw materials cost, be convenient to post-processing operation, and described acid binding agent is selected from K
2cO
3, Na
2cO
3, KOH, NaOH, triethylamine, at least one in pyridine.
Preferably, in the synthetic method of fluroxypyr ester of the present invention, the mol ratio of described acid binding agent and amino-3,5-bis-chloro-2, the 6-difluoro pyridines of 4-is 1.05-1.5:1.
Preferably, in the synthetic method of fluroxypyr ester of the present invention, described solvent is selected from least one in NMP, NEP, DMSO, sec-octyl alcohol, ethanol, methyl alcohol, toluene, hexanaphthene, and the amount used is 4-amino-3, the 2-4 of chloro-2, the 6-difluoro pyridine weight of 5-bis-doubly.
Beneficial effect of the present invention is:
1) route is simple, and easy to operate, cost is low;
2) adopt catalyzer and solvent with the use of time, reaction preference is improved, yield increase, reaction rate accelerates;
3) synthetic method mild condition of the present invention, and aftertreatment is simple, easy handling.
Embodiment
Below in conjunction with embodiment, the application is described in further detail.
fluroxypyr ethyl ester: the synthesis of ((the fluoro-2-pyridine of amino-3, the 5-bis-chloro-6-of 4-) oxygen base)-ethyl acetate
Embodiment 1: add 4-amino-3 in 400g toluene, 5-bis-chloro-2,6-difluoro pyridine 100.0g (0.50mol), ethyl glycollate 62.8g(0.60mol), sodium hydroxide 24.0g(0.60mol), be warming up to backflow, reaction 14h, cooling, washing, aftertreatment obtains product 112.2g, yield 79.3%.
Embodiment 2: add chloro-2, the 6-difluoro pyridine 100g (0.50mol) of 4-amino-3,5-bis-in 300g toluene, ethyl glycollate 62.8g(0.60mol), salt of wormwood 82.9g(0.60mol), tetrabutylammonium iodide 1.8g(0.005mol), be warming up to 100 DEG C, reaction 10h, adds water, thermally stratified layer, organic phase decrease temperature crystalline, filter, drying obtains product 126.3g, yield 89.2%.
Embodiment 3: add chloro-2, the 6-difluoro pyridine 100.0g (0.50mol) of 4-amino-3,5-bis-in 300g toluene, ethyl glycollate 62.8g(0.60mol), salt of wormwood 83.0g(0.60mol), Tetrabutyl amonium bromide 8.1g(0.025mol), be warming up to 80 DEG C, reaction 10h, adds water, thermally stratified layer, organic phase decrease temperature crystalline, filter, drying obtains product 127.7g, yield 90.2%.
Embodiment 4: add 4-amino-3 in 200gDMSO, 5-bis-chloro-2,6-difluoro pyridine 50g (0.25mol), ethyl glycollate 29.1g(0.28mol), sodium carbonate 29.7g(0.28mol), be warming up to 120 DEG C, reaction 12h, underpressure distillation goes out DMSO, add water, filter, drying obtains product 51.4g, yield 72.7%.
Embodiment 5: add chloro-2, the 6-difluoro pyridine 70g(0.35mol of 4-amino-3,5-bis-in 210g toluene), ethyl glycollate 43.7g(0.42mol), sodium carbonate 44.5g(0.28mol), benzyl triethyl ammonium bromide 1.9g(0.007mol) temperature rising reflux, reaction 11h, add water, thermally stratified layer, organic phase decrease temperature crystalline, filters, drying obtains product 88.9g, yield 89.7%.
fluroxypyr methyl esters: the synthesis of ((the fluoro-2-pyridine of amino-3, the 5-bis-chloro-6-of 4-) oxygen base)-methyl acetate
Embodiment 6: add chloro-2, the 6-difluoro pyridine 100.0g (0.50mol) of 4-amino-3,5-bis-in 200g toluene, methyl glycolate 49.5g(0.55mol), salt of wormwood 76.0g(0.55mol), Tetrabutyl amonium bromide 8.1g(0.025mol), be warming up to 100 DEG C, reaction 14h, adds water, thermally stratified layer, organic phase decrease temperature crystalline, filter, drying obtains product 122.8g, yield 91.3%.
Embodiment 7: add chloro-2, the 6-difluoro pyridine 50g (0.25mol) of 4-amino-3,5-bis-in 200g hexanaphthene, methyl glycolate 24.9g(0.28mol), sodium carbonate 29.7g(0.28mol), tetraethylammonium bromide 2.6g(0.013mol), be warming up to backflow, reaction 10h, add water, thermally stratified layer, organic phase decrease temperature crystalline, drying obtains product 67.3g, yield 89.2%.
Embodiment 8: add chloro-2, the 6-difluoro pyridine 50g (0.25mol) of 4-amino-3,5-bis-in 150gDMF, methyl glycolate 25.2g(0.28mol), sodium carbonate 29.7g(0.28mol), Tetraphenylphosphonium Bromide 2.1g(0.005mol), be warming up to 100 DEG C, reaction 8h, underpressure distillation goes out DMF, adds water, and filters, drying obtains product 59.7g, yield 88.7%.
The above; be only the present invention's preferably embodiment; but protection scope of the present invention is not limited thereto; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; be equal to according to technical scheme of the present invention and inventive concept thereof and replace or change, all should be encompassed within protection scope of the present invention.
Claims (8)
1. the synthetic method of fluroxypyr ester, is characterized in that, comprises the steps:
Add chloro-2, the 6-difluoro pyridines of 4-amino-3,5-bis-and acid binding agent in a solvent, be heated to 60-150 DEG C, drip ethyl glycolate, reaction 8-15h, after completing to condensation reaction, through adding water, layering, drying treatment obtain fluroxypyr ester;
The structural formula of described fluroxypyr ester is as follows:
r:1-8 alkyl;
The structure of described ethyl glycolate is as follows:
r:1-8 alkyl;
Described reaction process is as follows:
r:1-8 alkyl.
2. the synthetic method of fluroxypyr ester according to claim 1, is characterized in that, described synthetic method also comprises catalyzer; Described catalyzer is at least one in tetrabutylammonium iodide, tetraethyl ammonium iodide, 4 bromide, Tetrabutyl amonium bromide, tetrabutylammonium chloride, benzyl triethyl ammonium bromide, Tetraphenylphosphonium Bromide.
3. the synthetic method of fluroxypyr ester according to claim 2, is characterized in that, the mol ratio of described catalyzer and amino-3,5-bis-chloro-2, the 6-difluoro pyridines of 4-is 0.01-0.1:1.
4. the synthetic method of fluroxypyr ester according to claim 1, is characterized in that, the mol ratio of described ethyl glycolate and amino-3,5-bis-chloro-2, the 6-difluoro pyridines of 4-is 1.05-1.5:1.
5. the synthetic method of fluroxypyr ester according to claim 1, is characterized in that, described acid binding agent is K
2cO
3, Na
2cO
3, KOH, NaOH, triethylamine, at least one in pyridine.
6. the synthetic method of the fluroxypyr ester according to patent requirements 5, is characterized in that, the mol ratio of described acid binding agent and amino-3,5-bis-chloro-2, the 6-difluoro pyridines of 4-is 1.05-1.5:1.
7. the synthetic method of fluroxypyr ester according to claim 1, it is characterized in that, described solvent is at least one in NMP, NEP, DMSO, sec-octyl alcohol, ethanol, methyl alcohol, toluene, hexanaphthene, and consumption is 4-amino-3, the 2-4 of chloro-2, the 6-difluoro pyridine weight of 5-bis-doubly.
8. the synthetic method of the fluroxypyr ester according to claim 2 and 7, is characterized in that, described solvent is toluene, hexanaphthene.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106008334A (en) * | 2016-07-21 | 2016-10-12 | 四川福思达生物技术开发有限责任公司 | Preparation process of 4-amino-3, 5-dichloro-6-fluoro-2-ethyl oxy-acetate pyridine |
| CN106008333A (en) * | 2016-07-21 | 2016-10-12 | 四川福思达生物技术开发有限责任公司 | Preparation method of 4-amino-3, 5-dichloro-6-fluoro-2-ethyl oxy-acetate pyridine |
| CN109438333A (en) * | 2018-12-27 | 2019-03-08 | 青岛清原化合物有限公司 | A kind of pyridine oxygroup carboxylic ester derivative and preparation method thereof, Herbicidal combinations and application |
| CN113999169A (en) * | 2021-11-26 | 2022-02-01 | 江苏中旗科技股份有限公司 | Preparation method of fluroxypyr-meptyl |
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| US4108629A (en) * | 1973-03-19 | 1978-08-22 | The Dow Chemical Company | Herbicidal use of esters of aminohalopyridyloxy acids |
| CN101759632A (en) * | 2010-01-22 | 2010-06-30 | 武汉工程大学 | Fluorine chlorine pyridine oxygen dodecyl acetate compound and preparation method |
| CN103172561A (en) * | 2013-03-18 | 2013-06-26 | 永农生物科学有限公司 | Method for synthesizing [(4-amino-3,5-dichloro-6-fluoro-2-pyridinyl)oxy]acetic acid by using one-pot method |
-
2015
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Patent Citations (3)
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| US4108629A (en) * | 1973-03-19 | 1978-08-22 | The Dow Chemical Company | Herbicidal use of esters of aminohalopyridyloxy acids |
| CN101759632A (en) * | 2010-01-22 | 2010-06-30 | 武汉工程大学 | Fluorine chlorine pyridine oxygen dodecyl acetate compound and preparation method |
| CN103172561A (en) * | 2013-03-18 | 2013-06-26 | 永农生物科学有限公司 | Method for synthesizing [(4-amino-3,5-dichloro-6-fluoro-2-pyridinyl)oxy]acetic acid by using one-pot method |
Non-Patent Citations (1)
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106008334A (en) * | 2016-07-21 | 2016-10-12 | 四川福思达生物技术开发有限责任公司 | Preparation process of 4-amino-3, 5-dichloro-6-fluoro-2-ethyl oxy-acetate pyridine |
| CN106008333A (en) * | 2016-07-21 | 2016-10-12 | 四川福思达生物技术开发有限责任公司 | Preparation method of 4-amino-3, 5-dichloro-6-fluoro-2-ethyl oxy-acetate pyridine |
| CN106008334B (en) * | 2016-07-21 | 2019-02-01 | 四川福思达生物技术开发有限责任公司 | A kind of preparation process of the fluoro- 2- ethoxyacetic acid ethyl ester pyridine of the chloro- 6- of 4- amino -3,5- two |
| CN109438333A (en) * | 2018-12-27 | 2019-03-08 | 青岛清原化合物有限公司 | A kind of pyridine oxygroup carboxylic ester derivative and preparation method thereof, Herbicidal combinations and application |
| CN113999169A (en) * | 2021-11-26 | 2022-02-01 | 江苏中旗科技股份有限公司 | Preparation method of fluroxypyr-meptyl |
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