CN104513234B - A kind of method for synthesizing high-quality quizalofopPtefuryl - Google Patents
A kind of method for synthesizing high-quality quizalofopPtefuryl Download PDFInfo
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- CN104513234B CN104513234B CN201410828276.9A CN201410828276A CN104513234B CN 104513234 B CN104513234 B CN 104513234B CN 201410828276 A CN201410828276 A CN 201410828276A CN 104513234 B CN104513234 B CN 104513234B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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Abstract
The invention discloses a kind of method for synthesizing high-quality quizalofopPtefuryl, it includes：(R) 2 [4 (the quinoxaline epoxide of 6 chlorine 2) phenoxy group] ethyl propionates and tetrahydrofurfuryl alcohol are reacted under the effect of catalyst Dibutyltin oxide at 90 DEG C~180 DEG C.The high-quality quizalofopPtefuryl of more than 97% content, optical effective body more than 97% can be directly obtained without complicated post processing using the method for the present invention, reaction yield reaches more than 97%.
Description
Technical field
The invention belongs to pesticide synthesis field, and in particular to a kind of synthetic method of agricultural chemicals quizalofopPtefuryl.
Background technology
QuizalofopPtefuryl is the fragrant phenoxy developed by Uniroyal chemical companies (being now a CK Witco Crop part)
Carboxylic acids herbicide.It is a kind of new, efficient, spectrum to prevent and kill off gramineous weed weedicide.Its chemical name：(R)-2-[4-
(6- chloroquinoxalin-2-yloxies) benzene oxygen] propionic acid-(RS)-tetrahydrochysene chaff ester, structural formula：C22H21ClN2O5, molecular weight：428.87.
Physicochemical property：Sterling is deep yellow color liquid, i.e. crystallizable at room temperature.59 DEG C~68 DEG C of fusing point.Rat acute LD50 ＞
1012mg/kg.Have fish compared with high toxicity.
The synthetic method of quizalofopPtefuryl has following several：
Route 1：S- (-) p-toluenesulfonyl is obtained by S- (-) p-toluenesulfonyl ethyl lactate and tetrahydrofurfuryl alcohol reaction
Lactic acid chaff ester；Again quizalofopPtefuryl is obtained with the reaction of the chloro- 2- of 6- (4- hydroxyphenoxies) quinoline.
The technique tetrahydrofurfuryl alcohol is as raw material and solvent, and the reaction time is longer, intermediate S- (-) p-toluenesulfonyl breast
Sour chaff ester yield is relatively low, and the tetrahydrofurfuryl alcohol rate of recovery is relatively low, and cost is higher；And when synthesizing quizalofopPtefuryl, under basic conditions
The easy racemization of product, products obtained therefrom optical purity is not high, therefore less in industrialized production uses the method.
Route 2：Obtaining (R) -2- by 2,6- dichloro-quinoxalines and the reaction of (R) -2-4- hydroxyphenoxypropanoic acids, [4 (6- is chloro-
2- quinoxalines epoxide) phenoxy group] propionic acid, then directly synthesize obtaining quizalofopPtefuryl with tetrahydrofurfuryl alcohol.
The technique is used as Material synthesis intermediate (R) -2- [4 (chloro- 2- quinolines evils of 6- with (R) -2-4- hydroxyphenoxypropanoic acids
Quinoline epoxide) phenoxy group] propionic acid, yield is not high, and cost of material is high, and synthesis quizalofopPtefuryl is being carried out with esterification) when, raw material
Conversion is incomplete, and can not be removed containing moisture in recovery raw alcohol, therefore this method is not suitable for carrying out industrialized production.
Route 3：Obtained by S- (-) p-toluenesulfonyl ethyl lactate with the reaction of the chloro- 2- of 6- (4- hydroxyphenoxies) quinoline
(R) -2- [4 (the chloro- 2- quinoxalines epoxides of 6-) phenoxy group] ethyl propionate (Quizalotop-ethyl)；Again quinoline standing grain is obtained with tetrahydrofurfuryl alcohol reaction
Chaff ester.
The technique directly carries out ester exchange by intermediate (Quizalotop-ethyl) and tetrahydrofurfuryl alcohol and obtains product quizalofopPtefuryl.
In CN102584803A, using titanate ester catalyst, and non-polar organic solvent and tetrahydrofurfuryl alcohol are mixed solvent, the technique
Producing ethanol and organic solvent and tetrahydrofurfuryl alcohol can not be separated, and final influence is applied mechanically, therefore this method is not suitable for carrying out industry
Metaplasia is produced.
The content of the invention
The purpose of the present invention is that there is provided a kind of quizalofopPtefuryl for the various shortcomings that overcome in existing quizalofopPtefuryl synthetic route
Synthetic method.
The purpose of the present invention can be reached by following measures：
A kind of method for synthesizing high-quality quizalofopPtefuryl, it includes：(R) -2- [4 (the chloro- 2- quinoxalines epoxides of 6-) benzene oxygen
Base] ethyl propionate and tetrahydrofurfuryl alcohol reacted under the effect of catalyst Dibutyltin oxide at 90 DEG C~180 DEG C.
The reaction equation of the present invention is as follows：
The reaction of the present invention is simultaneously using tetrahydrofurfuryl alcohol as solvent and reactant.
In a kind of preferred scheme, (R) -2- [4 (the chloro- 2- quinoxalines epoxides of 6-) phenoxy group] ethyl propionates and tetrahydrofurfuryl alcohol
Mol ratio be 1：3~10.
The reaction of the present invention is using Dibutyltin oxide as catalyst, and the mole dosage of wherein catalyst Dibutyltin oxide is
(R) 0.1~1.0%, preferably the 0.1~0.5% of -2- [4 (the chloro- 2- quinoxalines epoxides of 6-) phenoxy group] ethyl propionate.
Reaction temperature of the present invention is preferably 100 DEG C~150 DEG C, needs to remove by-product by distillation or rectifying in course of reaction
Thing ethanol.The method that this method takes off ethanol using rectifying, using the high performance catalyst for being more suitable for this reaction, specific heating with
Under the cooperation of reaction condition, the quizalofopPtefuryl of high optical rotation is directly generated, yield is greatly improved.
Reaction time of the invention is preferably 4h~10h.
Signified high-quality quizalofopPtefuryl refers to that purity (including mass content and optical effective body content) exists in the present invention
More than 97% quizalofopPtefuryl.
In a kind of preferred scheme, precipitation after the completion of reaction, the tetrahydrofurfuryl alcohol of recovery can be applied mechanically as lower batch, add non-pole
Property organic solvent, activated carbon and water (at 40 DEG C~50 DEG C) insulation after, filter cleaner, be layered and precipitation after obtain high-quality quinoline standing grain
Chaff ester.
In a kind of preferred scheme, the method for the present invention comprises the following steps：To being provided with the reaction vessel of rectifying column
(R) -2- [4 (the chloro- 2- quinoxalines epoxides of 6-) phenoxy group] ethyl propionate, Dibutyltin oxide and tetrahydrofurfuryl alcohol is added, is warming up to
90 DEG C~180 DEG C (preferably 100 DEG C~150 DEG C) are reacted, and regulation reflux ratio keeps rectifying tower top temperature at 75 DEG C~85 DEG C,
Separate and collect ethanol, precipitation after reaction adds non-polar organic solvent, activated carbon and water after 40 DEG C~50 DEG C are incubated, mistake
Slag is filtered, is layered and obtains high-quality quizalofopPtefuryl after precipitation.
Non-polar organic solvent used in post processing is selected from benzene, toluene or dimethylbenzene, using toluene and dimethylbenzene as
It is good.The mass ratio of non-polar organic solvent, activated carbon and water can be 300~700：1~5：150~250.
The high-quality quinoline of more than 97% content, optical effective body more than 97% can be directly obtained using the method for the present invention
Standing grain chaff ester, reaction yield reaches more than 97%.
Embodiment
Embodiment 1
In the 1000ml four-hole bottles with rectifying column, Quizalotop-ethyl 144g (0.38mol), dibutyl oxidation are sequentially added
Tin 0.174g (0.0007mol) and tetrahydrofurfuryl alcohol 196g (1.90mol), heats up 140 DEG C, adjusts reflux ratio, it is ensured that tower top temperature
At 75 DEG C or so, collect after ethanol, backflow 8hr, negative pressure precipitation reclaims tetrahydrofurfuryl alcohol and applied mechanically as lower batch, addition toluene 500g,
Activated carbon 3g and water 200g, after 40 DEG C of -50 DEG C of insulation half an hour, pressure-filtering deslagging, layering, organic phase precipitation must obtain product
164g, content 97.2%, yield 97.8%.
Embodiment 2
In the 1000ml four-hole bottles with rectifying column, Quizalotop-ethyl 144g (0.38mol), Dibutyltin oxide are sequentially added
0.199g (0.0008mol) and tetrahydrofurfuryl alcohol 157g (1.52mol), heats up 130 DEG C, adjusts reflux ratio, it is ensured that tower top temperature exists
75 DEG C or so, collect after ethanol, backflow 8hr, negative pressure precipitation reclaims tetrahydrofurfuryl alcohol and applied mechanically as lower batch, addition dimethylbenzene 500g,
Activated carbon 3g and water 200g, after 40 DEG C of -50 DEG C of insulation half an hour, pressure-filtering deslagging, layering, organic phase precipitation must obtain product
163.8g, content 97.5%, yield 98%.
Claims (4)
1. a kind of method for synthesizing high-quality quizalofopPtefuryl, its feature comprises the following steps at it：To being provided with the anti-of rectifying column
Answer addition (R) -2- [4 (the chloro- 2- quinoxalines epoxides of 6-) phenoxy group] ethyl propionate, Dibutyltin oxide and tetrahydrochysene chaff in container
Alcohol, is warming up to 100 DEG C~150 DEG C and is reacted, and regulation reflux ratio keeps rectifying tower top temperature at 75 DEG C~85 DEG C, separates and receives
Collect ethanol, precipitation after reaction adds non-polar organic solvent, activated carbon and water after 40 DEG C~50 DEG C are incubated, filter cleaner, point
High-quality quizalofopPtefuryl is obtained after layer and precipitation；Wherein (R) -2- [4 (the chloro- 2- quinoxalines epoxides of 6-) phenoxy group] ethyl propionates with
The mol ratio of tetrahydrofurfuryl alcohol is 1：3~10；The mole dosage of catalyst Dibutyltin oxide is (R) -2- [4 (chloro- 2- quinolines evils of 6-
Quinoline epoxide) phenoxy group] ethyl propionate 0.1~1.0%.
2. according to the method described in claim 1, it is characterised in that the mole dosage of catalyst Dibutyltin oxide is (R) -2-
The 0.1~0.5% of [4 (the chloro- 2- quinoxalines epoxides of 6-) phenoxy group] ethyl propionate.
3. according to the method described in claim 1, it is characterised in that the reaction time is 4h~10h；The high-quality quizalofopPtefuryl
The quizalofopPtefuryl for being purity more than 97%.
4. according to the method described in claim 1, it is characterised in that the non-polar organic solvent is selected from benzene, toluene or diformazan
Benzene；The mass ratio of non-polar organic solvent, activated carbon and water is 300~700：1~5：150~250.
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| CN201410828276.9A CN104513234B (en) | 2014-12-28 | 2014-12-28 | A kind of method for synthesizing high-quality quizalofopPtefuryl |
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| CN201410828276.9A CN104513234B (en) | 2014-12-28 | 2014-12-28 | A kind of method for synthesizing high-quality quizalofopPtefuryl |
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| CN104513234B true CN104513234B (en) | 2017-07-14 |
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| CN105601623A (en) * | 2016-01-29 | 2016-05-25 | 合肥星宇化学有限责任公司 | Preparation method of quizalofop-p-tefuryl |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1670011A (en) * | 2004-03-17 | 2005-09-21 | 中国科学院成都有机化学有限公司 | Method for separating catalyst from ester interchange reaction solution |
| CN1676512A (en) * | 2004-03-29 | 2005-10-05 | 中国科学院成都有机化学有限公司 | Method for separating and purifying diaryl carbonate ester by rectification under vacuum |
| CN1840528A (en) * | 2005-04-01 | 2006-10-04 | 中国石油天然气集团公司 | Process for preparing N-formyl morpholine |
| CN101121736A (en) * | 2007-09-05 | 2008-02-13 | 江苏天禾药物研究所有限公司 | Method of preparing sucralose |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TR199802507T2 (en) * | 1996-06-03 | 1999-02-22 | Nissan Chemical Industries, Ltd. | Processes for producing the phenoxy propionic acid derivative. |
| CN100513383C (en) * | 2003-05-08 | 2009-07-15 | 中国石油天然气股份有限公司 | Method for separation purification of diaryl carbonate from transesterification reaction solution |
| CN102584803B (en) * | 2012-01-19 | 2014-12-10 | 江苏丰山集团有限公司 | Preparation method of high-content quizalofop-P-tefuryl |
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2014
- 2014-12-28 CN CN201410828276.9A patent/CN104513234B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1670011A (en) * | 2004-03-17 | 2005-09-21 | 中国科学院成都有机化学有限公司 | Method for separating catalyst from ester interchange reaction solution |
| CN1676512A (en) * | 2004-03-29 | 2005-10-05 | 中国科学院成都有机化学有限公司 | Method for separating and purifying diaryl carbonate ester by rectification under vacuum |
| CN1840528A (en) * | 2005-04-01 | 2006-10-04 | 中国石油天然气集团公司 | Process for preparing N-formyl morpholine |
| CN101121736A (en) * | 2007-09-05 | 2008-02-13 | 江苏天禾药物研究所有限公司 | Method of preparing sucralose |
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