CN107915686A - A kind of Quizalotop-ethyl and its intermediate 4（6 chlorine, 2 quinoxaline epoxide）The synthetic method of phenol - Google Patents
A kind of Quizalotop-ethyl and its intermediate 4（6 chlorine, 2 quinoxaline epoxide）The synthetic method of phenol Download PDFInfo
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
- C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
- C07D241/40—Benzopyrazines
- C07D241/44—Benzopyrazines 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 carbon atoms of the hetero ring
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Abstract
The present invention relates to a kind of synthetic method of Quizalotop-ethyl, its feature is that hydroquinone and sodium hydroxide reaction first prepare the sodium salt of hydroquinone, then with 2, the reaction of 6 dichloro-quinoxalines, obtains 4（6 chlorine, 2 quinoxaline epoxide）Phenol, then reacts to obtain Quizalotop-ethyl with p-methyl benzenesulfonic acid ethyl lactate.The synthesis technique optimizes former technique, and advantage is to be reacted and post-processed in organic solvent, reduces the alkalescence of reaction system, avoid aqueous phase reactions alkalescence it is too strong easily generation impurity the drawbacks of, reduce the hydrolysis of 2,6 dichloro-quinoxaline of raw material, make 4（6 chlorine, 2 quinoxaline epoxide）The content of phenol is to more than 98%, and yield reaches more than 92%, and follow-up synthetic reaction yield reaches more than 90%.
Description
Technical field
The present invention relates to pesticide synthesis technical field, and in particular to a kind of Quizalotop-ethyl and its intermediate 4-（Chloro- 2 quinolines of 6-
Quinoline epoxide）The synthetic method of phenol.
Background technology
Quizalotop-ethyl was selective herbicide after the bud that Japanese Nissan chemical industrial company develops, to 1 year and perennial standing grain
Undergraduate course weeds show it is powerful it is withered kill effect, to broad leaf crop safety, can be widely used for cotton, rape, peanut, soybean and more
The grassy weeds of crop such as kind broad-leaved vegetables are prevented and kill off, therefore with wide active compound synthesis and preparation processing prospect.
The synthetic route on Quizalotop-ethyl has two at present, and one is the generation side for raw material with 2,6- dichloro-quinoxalines
Reaction shown in formula 1, carries out directly or again esterification and obtains Quizalotop-ethyl, another route is to prepare 4-（Chloro- 2 quinolines of 6-
Quinoline epoxide）Phenol, reacts to obtain Quizalotop-ethyl with p-methyl benzenesulfonic acid ethyl lactate, such as equation 2.
Equation 1
R=H or ethyl.
Equation 2
Existing two methods are contrasted, the fracture of ester bond easily occurs in Willamson condensation courses are carried out for former approach,
The process yield that follow-up progress esterification is prepared Quizalotop-ethyl by acid is low.The latter carries out reaction and directly obtains product, step letter
Single, process is easily controllable, has greater advantage compared with the former, and be easy to implement industrialization.And the intermediate 4- in equation 2（6- is chloro-
2 quinoxaline epoxides）Influence of the phenol to synthesizing Quizalotop-ethyl quality is most important.
Up to now, the water that 2,6- dichloro-quinoxalines are participated in potassium hydroxide is mainly described in the prior art to be mutually etherified instead
Should, reaction system alkalescence is extremely strong, and Active Chlorine easily hydrolyzes in 2,6- dichloro-quinoxalines, influences etherification reaction yield, secondly
Since alkali concn is big, two molecules 2 are generated, 6- dichloro-quinoxalines and the impurity of a molecule hydroquinone are on the high side, etherification product content
It is relatively low；
The etherification reaction that 2,6- dichloro-quinoxalines are carried out with sodium hydroxide in toluene and DMF in the mixed solvents, the reaction are used
DMF, stronger to product dissolubility, 2,6- dichloro-quinoxalines are with base amount than about 1:5, bis ether impurity is on the high side, needs to use in addition
Frozen water is post-processed, and step is complicated, and frozen water can mix not disposable with solvent, have an impact to solvent recovery.
The content of the invention
For above technical background, it is an object of the invention to provide a kind of Quizalotop-ethyl and its intermediate 4-（6- chloro- 2
Quinoxaline epoxide）The synthetic method of phenol, first hydroquinone and sodium hydroxide reaction prepare the sodium salt of hydroquinone, then with 2,
6- dichloro-quinoxalines react, and obtain 4-（The chloro- 2 quinoxaline epoxides of 6-）Phenol, then reacts with p-methyl benzenesulfonic acid ethyl lactate
To Quizalotop-ethyl.The synthesis technique optimizes former technique, and advantage is to be reacted and post-processed in organic solvent, keeps away
Exempted from aqueous phase reactions alkalescence it is too strong easily generation impurity the drawbacks of.
Specifically, the concrete technical scheme of the application is as follows：
Synthesize 4-（The chloro- 2 quinoxaline epoxides of 6-）Phenol：Hydroquinone and sodium hydroxide are added under nitrogen protection, add toluene molten
The sodium salt of reaction generation hydroquinone at 65-95 DEG C is warming up to after solution, 99-105 DEG C is warming up to, the sodium salt of hydroquinone is added dropwise
Into the toluene solution of 2,6- dichloro-quinoxalines, insulation reaction, sampling detection, is less than 0.5% to 2,6- dichloro-quinoxalines content
When, mixed liquor is cooled to room temperature suction filtration, the salt that generation is reacted on filter cake is washed away with hot water, that is, obtains 4-（Chloro- 2 quinoxalines of 6-
Epoxide）Phenol.
Wherein the above reaction mass 2,6- dichloro-quinoxalines, hydroquinone, the molar ratio of sodium hydroxide are 2,6- bis-
Chloro-quinoxaline：Hydroquinone：Sodium hydroxide is 1：1.05-1.3：1.05-1.15.
The toluene dosage of wherein above-described dissolving hydroquinone and sodium hydroxide is the 5.0-8.0 of hydroquinone weight
Times.
Toluene dosage wherein in the toluene solution of the above 2,6- dichloro-quinoxalines is 2,6- dichloro-quinoxaline weight
10-13 times.
Above-described 4-（The chloro- 2 quinoxaline epoxides of 6-）The method of phenol synthesis Quizalotop-ethyl：By 4-（Chloro- 2 quinolines of 6-
Quinoline epoxide）Phenol and potassium carbonate mixing, add ethers nonpolar solvent to remove water, are warming up to 93~95 DEG C of reflux, are mixed backward to anhydrous
P-methyl benzenesulfonic acid ethyl lactate is added dropwise in compound, continues back flow reaction after being added dropwise, into the mixture system of reaction
4-（The chloro- 2 quinoxaline epoxides of 6-）Phenol residue is washed after being less than 0.1%, is depressurized after washing and is sloughed solvent, added anhydrous
Alcohol crystal obtains Quizalotop-ethyl.
Wherein, the molar ratio of material is 4- in above synthetic reaction（The chloro- 2 quinoxaline epoxides of 6-）Phenol：Potassium carbonate：To first
Benzene sulfonic acid ethyl lactate=1:1.5-3.0（The amount ratio of material）：1.05-1.15（The amount ratio of material）, synthesis reaction solvent dosage is
4-（The chloro- 2 quinoxaline epoxides of 6-）Phenol：Nonpolar solvent=1：20-25 （Mass ratio）.
In conclusion the method pair that the application provides, compared with existing method, advantage is the etherificate side of the application
Method carries out reaction in organic solvent toluene and prepares 4-（The chloro- 2 quinoxaline epoxides of 6-）Phenol, changes most phenol ginsengs in the prior art
With water phase Willamson etherificate mode, substantially reduce the alkalescence of reaction system, reduce the generation of impurity, subtract significantly
Raw material 2 is lacked, the hydrolysis of 6- dichloro-quinoxalines, improves the utilization rate of raw material, improve 4-（The chloro- 2 quinoxaline epoxides of 6-）Benzene
The yield of phenol.And this method easily facilitates operation, room temperature only need to be down to, leaches out solvent toluene, the etherate hot water of solid
Flushing, toluene recovery rate are high.
Catalyst 4- is made with potassium carbonate（The chloro- 2 quinoxaline epoxides of 6-）Phenol is reacted with p-methyl benzenesulfonic acid ethyl lactate
The process of Quizalotop-ethyl is obtained, reaction condition is optimized in this patent, shortens under the premise of Quizalotop-ethyl purity is not influenced
Reaction time.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, present invention specific examples below
Illustrate, but the present invention is only limitted to absolutely not these examples.
Embodiment 1：
11.6g is weighed under nitrogen protection（0.105mol）Hydroquinone and 4.3g（0.105mol）Sodium hydroxide, adds 60g toluene liters
To 85 DEG C of reaction 0.5h, cooling is transferred to spare in constant pressure funnel temperature.Nitrogen protection is lower to throw 20.2g（0.1mol）2,6- bis-
Chloro-quinoxaline and 220g toluene, are warming up to 100 DEG C, and the sodium salt of the hydroquinone prepared is added dropwise, and 1h is dripped off, and are protected after being added dropwise
Warm 6h, sampling tracking, 2,6- dichloro-quinoxaline contents are cooled to room temperature after being less than 0.5% qualification, hot water are used after draining filter cake
Washing to neutrality obtains 4-（The chloro- 2 quinoxaline epoxides of 6-）Phenol 25.3g, content 96.2%, yield 89.3%.
The lower 4- for throwing 0.1mol synthesis of nitrogen protection（The chloro- 2 quinoxaline epoxides of 6-）Phenol, 21.6g（0.156mol）Carbonic acid
Potassium, adds nonpolar solvent 710g, and heating band is left to anhydrous rear dropwise addition p-methyl benzenesulfonic acid ethyl lactate (0.105mol, 28.9g) 1h
The right side drips off rear back flow reaction 5h samplings tracking, and decompression steaming neat solvent after clear is washed to after qualified, adds 280g absolute ethyl alcohols
Crystallization, obtains Quizalotop-ethyl 33.6g, content 96.0%, yield 88.3%.
Embodiment 2：
14.3g is weighed under nitrogen protection（0.13mol）Hydroquinone and 4.7g（0.115mol）Sodium hydroxide, adds 72g toluene liters
To 85 DEG C of reaction 0.5h, cooling is transferred to spare in constant pressure funnel temperature.Nitrogen protection is lower to throw 20.2g（0.1mol）2,6- bis-
Chloro-quinoxaline and 220g toluene, are warming up to 100 DEG C, and the sodium salt of the hydroquinone prepared is added dropwise, and 1h is dripped off, and are protected after being added dropwise
Warm 6h, sampling tracking, 2,6- dichloro-quinoxaline contents are cooled to room temperature after being less than 0.5% qualification, hot water are used after draining filter cake
Washing to neutrality obtains 4-（The chloro- 2 quinoxaline epoxides of 6-）Phenol 25.7g, content 98.5%, yield 92.8%.
Nitrogen protection is lower to throw the 4- that 0.1mol synthesizes（The chloro- 2 quinoxaline epoxides of 6-）Phenol, 21.6g potassium carbonate, adds non-
After polar solvent 730g, heating band to anhydrous rear dropwise addition p-methyl benzenesulfonic acid ethyl lactate (0.115mol, 31.7g) 1h or so is dripped off
Back flow reaction 5h sampling tracking, until being washed to decompression after clear after qualified steams neat solvent, adds 230g absolute ethyl alcohols to crystallize,
Obtain Quizalotop-ethyl 34.3g, content 98.3%, yield 90.4%.
Embodiment 3：
12.7g is weighed under nitrogen protection（0.115mol）Hydroquinone and 4.3g（0.105mol）Sodium hydroxide, adds 75g toluene liters
To 85 DEG C of reaction 0.5h, cooling is transferred to spare in constant pressure funnel temperature.Nitrogen protection is lower to throw 20.2g（0.1mol）2,6- bis-
Chloro-quinoxaline and 250g toluene, are warming up to 100 DEG C, and the sodium salt of the hydroquinone prepared is added dropwise, and 1h is dripped off, and are protected after being added dropwise
Warm 6h, sampling tracking, 2,6- dichloro-quinoxaline contents are cooled to room temperature after being less than 0.5% qualification, hot water are used after draining filter cake
Washing to neutrality obtains 4-（The chloro- 2 quinoxaline epoxides of 6-）Phenol 25.8g, content 98.8%, yield 93.5%.
The lower 4- for throwing the above-mentioned synthesis of 0.1mol of nitrogen protection（The chloro- 2 quinoxaline epoxides of 6-）Phenol, 21.6g potassium carbonate, adds non-
After polar solvent 700g, heating band to anhydrous rear dropwise addition p-methyl benzenesulfonic acid ethyl lactate (0.115mol, 31.7g) 1h or so is dripped off
Back flow reaction 5h sampling tracking, is washed to decompression steaming neat solvent after clear, adds 200g absolute ethyl alcohols to crystallize, obtain after qualified
Quizalotop-ethyl 34.7g, content 98.1%, yield 91.4%.
Embodiment 4：
12.7g is weighed under nitrogen protection（0.115mol）Hydroquinone and 4.5g（0.11mol）Sodium hydroxide, adds 75g toluene liters
To 85 DEG C of reaction 0.5h, cooling is transferred to spare in constant pressure funnel temperature.Nitrogen protection is lower to throw 20.2g（0.1mol）2,6- bis-
Chloro-quinoxaline and 220g toluene, are warming up to 100 DEG C, and the sodium salt of the hydroquinone prepared is added dropwise, and 1h is dripped off, and are protected after being added dropwise
Warm 6h, sampling tracking, 2,6- dichloro-quinoxaline contents are cooled to room temperature after being less than 0.5% qualification, hot water are used after draining filter cake
Washing to neutrality obtains 4-（The chloro- 2 quinoxaline epoxides of 6-）Phenol 25.8g, content 98.4%, yield 93.3%.
Nitrogen protection is lower to throw the 4- that step reaction obtains on 0.1mol（The chloro- 2 quinoxaline epoxides of 6-）Phenol, 21.6g potassium carbonate,
Add nonpolar solvent 700g, heating band to anhydrous rear dropwise addition p-methyl benzenesulfonic acid ethyl lactate (0.115mol, 31.7g) 1h or so
Rear back flow reaction 5h samplings tracking is dripped off, decompression steaming neat solvent after clear is washed to after qualified, adds 200g absolute ethyl alcohol knots
Crystalline substance, obtains Quizalotop-ethyl 34.7g, content 98.6%, yield 91.7%.
Embodiment 5：
26.4g is weighed under nitrogen protection（0.24mol）Hydroquinone and 9.4g（0.23mol）Sodium hydroxide, adds 150g toluene liters
To 85 DEG C of reaction 0.5h, cooling is transferred to spare in constant pressure funnel temperature.Nitrogen protection is lower to throw 40.4g（0.2mol）2,6- bis-
Chloro-quinoxaline and 440g recycling toluene phases, are warming up to 101 DEG C, the sodium salt of the hydroquinone prepared are added dropwise, 1h is dripped off, and is dripped
6h is kept the temperature after finishing, sampling tracking 2,6- dichloro-quinoxalines content is cooled to room temperature after being less than 0.5%, drains filter cake, recycle first
Benzene phase, filter cake are washed to neutrality with hot water and obtain 4-（The chloro- 2 quinoxaline epoxides of 6-）Phenol 25.6g, content 98.1%, yield
92.0%。
Nitrogen protection is lower to throw the 4- that synthesis is walked on 0.1mol（The chloro- 2 quinoxaline epoxides of 6-）Phenol, 21.6g potassium carbonate, adds non-
Polar solvent 700g, heating band to anhydrous rear p-methyl benzenesulfonic acid ethyl lactate (0.115mol, 31.7g) 1h or so that is added dropwise drip off
Back flow reaction 10h samplings tracking afterwards, is washed to decompression steaming neat solvent after clear, adds 230g absolute ethyl alcohols to crystallize after qualified,
Obtain Quizalotop-ethyl 35.0g, content 97.9%, yield 91.9%.
Claims (7)
- A kind of 1. 4-（The chloro- 2 quinoxaline epoxides of 6-）The synthetic method of phenol, it is characterised in that add under nitrogen protection to benzene Diphenol and sodium hydroxide, add toluene to be warming up to the sodium salt of reaction generation hydroquinone at 65-95 DEG C after dissolving, are warming up to 99-105 DEG C, the sodium salt of hydroquinone is added dropwise in the toluene solution of 2,6- dichloro-quinoxalines, insulation reaction, sampling detection, to 2,6- When dichloro-quinoxaline content is less than 0.5%, mixed liquor is cooled to room temperature suction filtration, the salt that generation is reacted on filter cake is washed away with hot water, Obtain 4-（The chloro- 2 quinoxaline epoxides of 6-）Phenol.
- A kind of 2. 4- as claimed in claim 1（The chloro- 2 quinoxaline epoxides of 6-）The synthetic method of phenol, it is characterised in that：Reaction Material 2,6- dichloro-quinoxalines, hydroquinone, the molar ratio of sodium hydroxide are 2,6- dichloro-quinoxalines：Hydroquinone：Hydroxide Sodium is 1：1.05-1.3：1.05-1.15.
- A kind of 3. 4- as claimed in claim 1 or 2（The chloro- 2 quinoxaline epoxides of 6-）The synthetic method of phenol, it is characterised in that： The dissolving hydroquinone and the toluene dosage of sodium hydroxide are 5.0-8.0 times of hydroquinone weight.
- A kind of 4. 4- as claimed in claim 1 or 2（The chloro- 2 quinoxaline epoxides of 6-）The synthetic method of phenol, it is characterised in that： Toluene dosage in the toluene solution of 2,6- dichloro-quinoxalines is 10-13 times of 2,6- dichloro-quinoxaline weight.
- A kind of 5. 4- using described in claim 1 or 2（The chloro- 2 quinoxaline epoxides of 6-）The method of phenol synthesis Quizalotop-ethyl, It is characterized in that, by 4-（The chloro- 2 quinoxaline epoxides of 6-）Phenol and potassium carbonate mixing, add ethers nonpolar solvent be warming up to 93~ 95 DEG C of reflux band water, are added dropwise p-methyl benzenesulfonic acid ethyl lactate into anhydrous backward mixture, continue back flow reaction after being added dropwise, The sampling of reaction mixture system tracks to raw material 4-（The chloro- 2 quinoxaline epoxides of 6-）Phenol residue is cooled to 70 DEG C after being less than 0.1% Left and right is washed, and is depressurized after washing and is sloughed solvent, adds absolute ethyl alcohol crystallization to obtain Quizalotop-ethyl.
- 6. one kind as claimed in claim 5 utilizes 4-（The chloro- 2 quinoxaline epoxides of 6-）The method of phenol synthesis Quizalotop-ethyl, its It is characterized in that, the molar ratio of material is 4- in synthetic reaction（The chloro- 2 quinoxaline epoxides of 6-）Phenol：Potassium carbonate：P-methyl benzenesulfonic acid breast Acetoacetic ester=1:1.5-3.0：1.05-1.15.
- 7. one kind as claimed in claim 5 utilizes 4-（The chloro- 2 quinoxaline epoxides of 6-）The method of phenol synthesis Quizalotop-ethyl, its It is characterized in that, the mass ratio of synthesis reaction solvent dosage is 4-（The chloro- 2 quinoxaline epoxides of 6-）Phenol：Nonpolar solvent=1：20- 25。
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997046538A1 (en) * | 1996-06-03 | 1997-12-11 | Nissan Chemical Industries, Ltd. | Processes for producing phenoxy propionic acid derivatives |
| CN101333194A (en) * | 2007-06-29 | 2008-12-31 | 山东京博控股发展有限公司 | Method for preparing quizalofop-p-ethyl |
| CN101531640A (en) * | 2009-04-14 | 2009-09-16 | 北京颖泰嘉和科技股份有限公司 | Preparation method of quizalofop-p-ethyl with high optical content |
| CN101875642A (en) * | 2010-06-13 | 2010-11-03 | 山东京博控股发展有限公司 | Synthetic method of 4-(6-chloroquinoxalin-2-yloxy) phenol |
| 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 |
-
2017
- 2017-09-07 CN CN201710801531.4A patent/CN107915686A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997046538A1 (en) * | 1996-06-03 | 1997-12-11 | Nissan Chemical Industries, Ltd. | Processes for producing phenoxy propionic acid derivatives |
| CN101333194A (en) * | 2007-06-29 | 2008-12-31 | 山东京博控股发展有限公司 | Method for preparing quizalofop-p-ethyl |
| CN101531640A (en) * | 2009-04-14 | 2009-09-16 | 北京颖泰嘉和科技股份有限公司 | Preparation method of quizalofop-p-ethyl with high optical content |
| CN101875642A (en) * | 2010-06-13 | 2010-11-03 | 山东京博控股发展有限公司 | Synthetic method of 4-(6-chloroquinoxalin-2-yloxy) phenol |
| 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 |
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