CN103787962A - Fluroxypyr sec-octyl ester synthesizing method - Google Patents
Fluroxypyr sec-octyl ester synthesizing method Download PDFInfo
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- CN103787962A CN103787962A CN201410083920.4A CN201410083920A CN103787962A CN 103787962 A CN103787962 A CN 103787962A CN 201410083920 A CN201410083920 A CN 201410083920A CN 103787962 A CN103787962 A CN 103787962A
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- fluroxypyr
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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 Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A fluroxypyr sec-octyl ester synthesizing method comprises the following steps that (1) 4-amino-3,5-dichloro-6-fluorine-2-pyridine potassium phenoxide is dissolved in N-methyl pyrrolidone, an excessive amount of methyl chloroacetate is added into the solution, and stirring and temperature rising are conducted for reaction, wherein the reaction time is 5-5.5 hours and the reaction temperature is 52 DEG C-55 DEG C; (2) an excessive amount of sec-octyl ester and 4-amino-3,5-dichloro-6-fluorine-2 pyridine oxygen methyl acetate are mixed and stirred and o.5%-1% of butyl titanate is added, wherein the alcohol and ester molar ratio is 2-2.3:1, the reaction temperature is 115 DEG C and the reaction time is 4-4.5 hours; after reaction ends, fluroxypyr sec-octyl ester is obtained.
Description
Technical field
The present invention relates to the synthetic method of the secondary monooctyl ester of a kind of fluroxypyr.
Background technology
The chemical name of the secondary monooctyl ester of fluroxypyr is 4-amino-3, the fluoro-2-pyridine of the chloro-6-of 5-bis-fluoroacetic acid (1-meptyl ester), and fusing point 56-57 ℃, under normal temperature, shelf stable for periods is 2 years, decomposes higher than fusing point, industrial former medicine is the white crystal with soap smell.The secondary monooctyl ester of fluroxypyr is that one has interior suction conductivity weedicide, can be used as cauline leaf processing after seedling, is applicable to various crop, as winter crops such as wheat, barley, corn, orchards, prevents and kill off multiple malignant weed ashamed, as Herba Galii Teneri, water peanut, Herba seu Flos Convolvuli arvensis etc.The domestic research report having its purposes and using method of the secondary monooctyl ester product of fluroxypyr, there is not yet the report of its synthetic method.
Summary of the invention
technical problem
In view of this, the technical problem to be solved in the present invention is, provides that a kind of yield is high, the secondary monooctyl ester synthetic method of the fluroxypyr of environmental protection.
solution
In order to solve the problems of the technologies described above, the invention provides the secondary monooctyl ester synthetic method of a kind of fluroxypyr, comprise the steps,
(1) 4-amino-3, the fluoro-2-pyridol of the chloro-6-of 5-bis-potassium is dissolved in N-Methyl pyrrolidone, adds excess chlorine methyl acetate to stir and heats up, and reacts, and the reaction times is 5～5.5h, and temperature of reaction is 52～55 ℃;
(2) by excessive secondary octanol and 4-amino-3, the fluoro-2-pyridine of the chloro-6-of 5-bis-fluoroacetic acid methyl esters mix and blend, alcohol ester mol ratio 2～2.3:1, adding consumption is the butyl (tetra) titanate of 0.5%-1%, 115 ℃ of temperature of reaction, in 4～4.5 hours reaction times, make the secondary monooctyl ester of fluroxypyr after having reacted.
Preferably, in described step (1), described N-Methyl pyrrolidone and described 4-amino-3, the fluoro-2-pyridol of the chloro-6-of 5-bis-potassium mol ratio is 8～9:1, described 4-amino-3, the fluoro-2-pyridol of the chloro-6-of 5-bis-potassium is 1:1.1～1.2 with the mol ratio of reacting of described methyl chloroacetate.
beneficial effect
The invention provides that a kind of yield is high, the secondary monooctyl ester synthetic method of the fluroxypyr of environmental protection.
Embodiment
Embodiment
4-amino-3, the fluoro-2-pyridol of the chloro-6-of 5-bis-potassium is dissolved in N-Methyl pyrrolidone (NMP), and underpressure distillation dewaters to 500ppm.Add excess chlorine methyl acetate to stir and heat up, holding temperature is treated 4-amino-3, the fluoro-2-pyridol of the chloro-6-of 5-bis-potassium complete reaction, reaction times is 5～5.5h, temperature of reaction is 52～55 ℃, steams last methyl chloroacetate after having reacted, and in reaction solution, pours suitable quantity of water into, be stirred and heated to 80～85 ℃ and maintain 1～2h, after put into frozen water crystallisation by cooling, treat that product separates out filtration washing completely, after oven dry white solid, yield 95.6%, content 99.2%.
N-Methyl pyrrolidone (NMP) and 4-amino-3, the fluoro-2-pyridol of the chloro-6-of 5-bis-potassium mol ratio 8～9:1,4-amino-3, the fluoro-2-pyridol of the chloro-6-of 5-bis-potassium is 1:1.1～1.2 with the mol ratio of reacting of methyl chloroacetate.
By excessive secondary octanol and 4-amino-3, the fluoro-2-pyridine of the chloro-6-of 5-bis-fluoroacetic acid methyl esters mix and blend, alcohol ester mol ratio 2～2.3:1, micro-moisture contained in material is removed in underpressure distillation, add a small amount of transesterification catalyst butyl (tetra) titanate, catalyst levels is 0.5%-1%, be heated to 115 ℃, limit coronite decompression steams the methyl alcohol of generation, reaction times is 4～4.5 hours, adds suitable quantity of water component distillation to take remaining secondary octanol out of after question response is complete, and cooled and filtered obtains product, content 98.7%, yield 96.8%.
The above; be only the specific embodiment of the present invention, but protection scope of the present invention is not limited to this, any be familiar with those skilled in the art the present invention disclose technical scope in; can expect easily changing or replacing, within all should being encompassed in protection scope of the present invention.Therefore, protection scope of the present invention should described be as the criterion with the protection domain of claim.
Claims (2)
1. the secondary monooctyl ester synthetic method of fluroxypyr, is characterized in that, comprise the steps,
(1) 4-amino-3, the fluoro-2-pyridol of the chloro-6-of 5-bis-potassium is dissolved in N-Methyl pyrrolidone, adds excess chlorine methyl acetate to stir and heats up, and reacts, and the reaction times is 5～5.5h, and temperature of reaction is 52～55 ℃;
(2) by excessive secondary octanol and 4-amino-3, the fluoro-2-pyridine of the chloro-6-of 5-bis-fluoroacetic acid methyl esters mix and blend, alcohol ester mol ratio 2～2.3:1, adding consumption is the butyl (tetra) titanate of 0.5%-1%, 115 ℃ of temperature of reaction, in 4～4.5 hours reaction times, make the secondary monooctyl ester of fluroxypyr after having reacted.
2. synthetic method according to claim 1, it is characterized in that, in described step (1), described N-Methyl pyrrolidone and described 4-amino-3, the fluoro-2-pyridol of the chloro-6-of 5-bis-potassium mol ratio is 8～9:1, described 4-amino-3, the fluoro-2-pyridol of the chloro-6-of 5-bis-potassium is 1:1.1～1.2 with the mol ratio of reacting of described methyl chloroacetate.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410083920.4A CN103787962A (en) | 2014-03-07 | 2014-03-07 | Fluroxypyr sec-octyl ester synthesizing method |
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| CN201410083920.4A CN103787962A (en) | 2014-03-07 | 2014-03-07 | Fluroxypyr sec-octyl ester synthesizing method |
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Cited By (3)
| 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 |
| CN106187872A (en) * | 2016-07-21 | 2016-12-07 | 四川福思达生物技术开发有限责任公司 | A kind of preparation method of fluroxypyr |
Citations (2)
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|---|---|---|---|---|
| CN1031566C (en) * | 1990-02-09 | 1996-04-17 | 道伊兰科公司 | Preparation of higher alkyl esters of carboxylic acids |
| 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 |
-
2014
- 2014-03-07 CN CN201410083920.4A patent/CN103787962A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1031566C (en) * | 1990-02-09 | 1996-04-17 | 道伊兰科公司 | Preparation of higher alkyl esters of carboxylic acids |
| 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 (2)
| Title |
|---|
| JI-YE HU,等: "Residue Analysis of Fluroxypyr-meptyl in Wheat and Soil by GC–ECD", 《CHROMATOGRAPHIA》, vol. 74, no. 34, 15 May 2011 (2011-05-15), pages 291 - 296, XP019926175, DOI: 10.1007/s10337-011-2050-2 * |
| QIN TIAN,等: "Direct Enantiomeric Separation of Chiral Pesticides by LC on Amylose Tris(3,5-dimethylphenylcarbamate) Stationary Phase under Reversed Phase Conditions", 《CHROMATOGRAPHIA》, vol. 71, no. 910, 17 April 2010 (2010-04-17), pages 855 - 865, XP019810154 * |
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 |
| CN106187872A (en) * | 2016-07-21 | 2016-12-07 | 四川福思达生物技术开发有限责任公司 | A kind of preparation method of fluroxypyr |
| CN106187872B (en) * | 2016-07-21 | 2018-12-04 | 四川福思达生物技术开发有限责任公司 | A kind of preparation method of fluroxypramide |
| 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 |
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Application publication date: 20140514 |