CN107325044A - A kind of preparation method of herbicide triclopyr butoxyethyl ester - Google Patents
A kind of preparation method of herbicide triclopyr butoxyethyl ester Download PDFInfo
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- CN107325044A CN107325044A CN201710553633.9A CN201710553633A CN107325044A CN 107325044 A CN107325044 A CN 107325044A CN 201710553633 A CN201710553633 A CN 201710553633A CN 107325044 A CN107325044 A CN 107325044A
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- butoxyethyl ester
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- triclopyr butoxyethyl
- herbicide
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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
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/64—One oxygen atom attached in position 2 or 6
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Abstract
The invention discloses a kind of preparation method of herbicide triclopyr butoxyethyl ester, belong to field of pesticide chemistry, implement as steps described below：Using trichloro pyridyl sodium alcoholate and monoxone as raw material, through reacted under the conditions of catalyst 1 and organic solvent picolinic acid class herbicide trichlopyr (Triclopyr) be raw material, trichlopyr is prepared into acyl chlorides, afterwards in catalyst 2, the method that condensation reaction prepares triclopyr butoxyethyl ester is carried out under the conditions of Fu's acid agent and organic solvent with 2 butyl cellosolves.The content of triclopyr butoxyethyl ester is 95.2%, yield 85.6%, synthesizes easily operated, post processing is easy, wastewater flow rate is few, is adapted to prepare herbicide triclopyr butoxyethyl ester.
Description
Technical field
The present invention relates to a kind of preparation method of picolinic acid class herbicide triclopyr butoxyethyl ester, specifically relate to
And to one kind using picolinic acid class herbicide trichlopyr and butoxy ethanol as raw material, under catalyst and dehydrating agent
The method that the step of condensation reaction two prepares triclopyr butoxyethyl ester is carried out, belongs to field of agrochemicals.
Background technology
Triclopyr butoxyethyl ester is picolinic acid class systemic herbicide, available for preventing and kill off forest farm shrub and wealthy
Leaf weeds, open forest zone firebreak, it can also be used in soybean crops.Preparation has missible oil.The mechanism of the kind can be by plant
Leaf and root absorb, and conduction plant is whole, by acting on nucleic acid metabolism, and plant is produced excessive nucleic acid, some are organized
It is transformed into separate living tissue, and causes blade, stem and root growth deformity, causes plant dead.Be bare place forest farm and grassland it is excellent
Elegant herbicide.
WO2010023679A2 reports the synthetic method of triclopyr butoxyethyl ester, is specifically with trichloropyridine
Sodium alkoxide is raw material, and trichlopyr methyl esters is generated with methyl chloroacetate etherification reaction, through hydrolysis generation trichlopyr sodium,
Be acidified to obtain its acids, after under sulfuric acid catalysis and ethylene glycol monobutyl ether prepare herbicide triclopyr butoxyethyl ester, instead
It should have the disadvantage cumbersome, more methanol be produced during hydrolysis, esterification makees solvent using toluene, not meeting prepared by green will
Ask, not environmentally.CN102295597A is reported obtains intermediate monoxone butoxy second by butoxy ethanol and chloroethene are etherified
Ester, is condensed to obtain triclopyr butoxyethyl ester with trichloro pyridyl sodium alcoholate afterwards, and the route has technique simple, and yield is higher
Using toxic solvents such as solid acid and toluene in feature, but reaction, cost is higher, does not meet environment friendly agricultural technological requirement.
The content of the invention
Simple present invention aims at a kind of technique is provided, yield is higher, environmental protection and economic trichlopyr fourth oxygen
The preparation method of base ethyl ester.
The present invention technical solution be：
A kind of preparation method of herbicide triclopyr butoxyethyl ester, including following several steps：
Trichloro pyridyl sodium alcoholate and solvent 1 are added in the reactor, and stirring is lower to add catalyst 1, and chloroacetic solvent 1 is added dropwise
Solution, back flow reaction 4-6h adds water after cooling, hydrochloric acid acidifying, ethyl acetate extraction, and after organic layer washing, precipitation removes solvent
Obtain intermediate trichlopyr；
Raw material trichlopyr and oxalyl chloride are added in reaction bulb, catalyst 2 is added, rear room temperature reaction is stayed overnight, instead
Answer liquid precipitation to remove and trichlorine pyrrole oxygen chloroacetic chloride is obtained after oxalyl chloride, be directly used in next step；
Raw material butoxy ethanol and solvent 2 are added in reaction bulb, ice bath stirring is lower to add acid binding agent and catalyst 3
Afterwards, the solution of solvent 2 of trichlorine pyrrole oxygen chloroacetic chloride is added dropwise, 3.0-5.0h is reacted at room temperature, reaction is finished, and reaction solution is successively with watery hydrochloric acid
With saturated common salt water washing, desolvation obtains triclopyr butoxyethyl ester after organic layer is dried；
It is preferred that, described trichloro pyridyl sodium alcoholate and chloroacetic mol ratio are 1:1-1:1.4.
It is preferred that, described trichlopyr and the mol ratio of oxalyl chloride are 1:1-1:4.
It is preferred that, described raw material butoxy ethanol and triethylamine mol ratio are 1:0.8-1:1.2.
It is preferred that, described butoxy ethanol and trichlorine pyrrole oxygen acetyl cl molar ratio：1:1-1:1.5.
It is preferred that, described solvent 1 is DMF, acetonitrile or DMA, and solvent 2 is two
Chloromethanes, chloroform or tetrahydrofuran.
It is preferred that, described acid binding agent is triethylamine or pyridine.
It is preferred that, trichlopyr temperature is prepared for 130-150 DEG C.
It is preferred that, the catalyst 1 is PEG-400；Catalyst 2 is N,N-dimethylformamide；Catalyst 3 is 4- diformazans
Aminopyridine.
The present invention has the following advantages that compared with prior art：
1) synthesis trichlorine gives a tongue-lashing the reaction of fluoroacetic acid and shortens step, and one is reduced to by WO2010023679A2 two steps reported
Step, improves reaction yield.
2) compared with patent CN102295597A, esterification technique is simple to operate, and reaction condition is gentle, it is to avoid use higher boiling
And have the toluene of certain toxicity, it is easy to remove in post processing using dichloromethane, pollutes small.
3) whole piece route total recovery is higher, is 93.9%.Wastewater flow rate is few, catalyst, and acid binding agent and organic solvent can be returned
Receive and utilize, environmental protection.
4) compared with patent CN102295597A, catalyst used in whole piece route and acid binding agent cost are low, it is to avoid make
With the reagent costly such as solid acid and triethyl benzyl ammonia chloride, economical feature.
With reference to embodiment, the present invention will be further described.
Embodiment
Following examples are intended to illustrate invention rather than limitation of the invention further.
The present invention reaction equation be：
Embodiment 1
Equipped with motor, 22g (0.1mol) trichloro pyridyl sodium alcoholate is added in three mouthfuls of reaction bulbs of condenser pipe and dropping funel
With DMF 100mL, stirring is lower to add 0.2g phase transfer catalyst PEG-400, is added dropwise contains 9.4g afterwards
(0.1mol) chloroacetic 20mLN, dinethylformamide liquid finishes and is warming up to 140 DEG C, reacts 4.0h, cools down, and adds
400mL frozen water, watery hydrochloric acid is acidified to pH=2-3, is extracted 4 times with 100mL ethyl acetate, merges organic layer, 100mL saturated common salts
Twice, precipitation obtains white powder trichlopyr, content after product, ethyl alcohol recrystallization to water washing after organic layer is dried
98.2%, yield 95.3%.
In the trichlopyr and 80mL dichloromethane of drying addition 25.4g (0.1mol) in single port bottle, 0.3mol grass
Acyl chlorides, is added dropwise the DMF of catalytic amount.Room temperature reaction is stayed overnight, and excessive dichloromethane and oxalyl is removed under reduced pressure
Chlorine, product is directly used in next step.
In three mouthfuls of reaction bulbs equipped with agitator and dropping funel add 11.8g (0.1mol) butoxy ethanols and
120mL dichloromethane, ice bath stirring is lower to add 10.1g (0.1mol) triethylamines and 0.2g DMAPs, and dropwise addition contains
The 25mL dichloromethane solutions of 32.6g (0.12mol) trichlorine pyrrole oxygen chloroacetic chloride, about 0.5h is dripped off, and reacts at room temperature 3.0h, reaction solution
Washed twice with 60mL watery hydrochloric acid, 60mL saturated aqueous common salts are washed twice, Na2SO4Dry, precipitation removes solvent and obtains light yellow liquid
Body triclopyr butoxyethyl ester, content 95.2%, yield 98.6%.
Embodiment 2
Equipped with motor, 22g (0.1mol) trichloro pyridyl sodium alcoholate is added in three mouthfuls of reaction bulbs of condenser pipe and dropping funel
With DMA 100mL, stirring is lower to add 0.2g phase transfer catalyst PEG-400, is added dropwise contains 9.4g afterwards
(0.1mol) chloroacetic 20mLN, N- dimethyl acetamide liquid, finish and are warming up to 140 DEG C, react 5.0h, cool down, and add
400mL frozen water, watery hydrochloric acid is acidified to pH=2-3, is extracted 4 times with 110mL ethyl acetate, merges organic layer, 100mL saturated common salts
Twice, precipitation obtains white powder trichlopyr, content after product, ethyl alcohol recrystallization to water washing after organic layer is dried
96.3%, yield 92.3%.
In the trichlopyr and 80mL dichloromethane of drying addition 25.4g (0.1mol) in single port bottle, 0.3mol grass
Acyl chlorides, is added dropwise the DMF of catalytic amount.Room temperature reaction is stayed overnight, and excessive dichloromethane and oxalyl is removed under reduced pressure
Chlorine, product is directly used in next step.
In three mouthfuls of reaction bulbs equipped with agitator and dropping funel add 11.8g (0.1mol) butoxy ethanols and
100mL chloroforms, ice bath stirring is lower to add 10.1g (0.1mol) triethylamines and 0.2g DMAPs, and dropwise addition contains
The 25mL dichloromethane solutions of 32.6g (0.12mol) trichlorine pyrrole oxygen chloroacetic chloride, about 0.5h is dripped off, and reacts at room temperature 4.0h, reaction solution
Washed twice with 60mL watery hydrochloric acid, 60mL saturated aqueous common salts are washed twice, Na2SO4Dry, precipitation removes solvent and obtains light yellow liquid
Body triclopyr butoxyethyl ester, content 92.2%, yield 90.5%.
Technical staff will be understood that the change of approach described herein and/or the change of methods known in the art can
Suitable for this method.
Claims (9)
1. a kind of preparation method of herbicide triclopyr butoxyethyl ester, it is characterised in that including following several steps：
Trichloro pyridyl sodium alcoholate and solvent 1 are added in the reactor, and stirring is lower to add catalyst 1, chloroacetic solvent 1 is added dropwise molten
Liquid, back flow reaction 4-6h adds water after cooling, hydrochloric acid acidifying, ethyl acetate extraction, and after organic layer washing, precipitation removes solvent and obtained
Intermediate trichlopyr；
Raw material trichlopyr and oxalyl chloride are added in reaction bulb, catalyst 2 is added, rear room temperature reaction is stayed overnight, reaction solution
Precipitation, which is removed, obtains trichlorine pyrrole oxygen chloroacetic chloride after oxalyl chloride, be directly used in next step；
Raw material butoxy ethanol and solvent 2 are added in reaction bulb, ice bath stirring is lower to be added after acid binding agent and catalyst 3, drop
Plus the solution of solvent 2 of trichlorine pyrrole oxygen chloroacetic chloride, 3.0-5.0h is reacted at room temperature, reaction is finished, reaction solution with watery hydrochloric acid and is satisfied successively
And brine It, desolvation obtains triclopyr butoxyethyl ester after organic layer is dried；
2. a kind of preparation method of herbicide triclopyr butoxyethyl ester according to claim 1, its feature exists
In：Described trichloro pyridyl sodium alcoholate and chloroacetic mol ratio are 1:1-1:1.4.
3. a kind of preparation method of herbicide triclopyr butoxyethyl ester according to claim 1, its feature exists
In：Described trichlopyr and the mol ratio of oxalyl chloride are 1:1-1:4.
4. a kind of preparation method of herbicide triclopyr butoxyethyl ester according to claim 1, its feature exists
In：Described raw material butoxy ethanol and triethylamine mol ratio are 1:0.8-1:1.2.
5. a kind of preparation method of herbicide triclopyr butoxyethyl ester according to claim 1, its feature exists
In：Described butoxy ethanol and trichlorine pyrrole oxygen acetyl cl molar ratio：1:1-1:1.5.
6. a kind of preparation method of herbicide triclopyr butoxyethyl ester according to claim 1, its feature exists
In：Described solvent 1 is DMF, acetonitrile or DMA, and solvent 2 is dichloromethane, trichlorine
Methane or tetrahydrofuran.
7. a kind of preparation method of herbicide triclopyr butoxyethyl ester according to claim 1, its feature exists
In：Described acid binding agent is triethylamine or pyridine.
8. a kind of preparation method of herbicide triclopyr butoxyethyl ester according to claim 1, its feature exists
In：Trichlopyr temperature is prepared for 130-150 DEG C.
9. a kind of preparation method of herbicide triclopyr butoxyethyl ester according to claim 1, its feature exists
In：The catalyst 1 is PEG-400；Catalyst 2 is N,N-dimethylformamide；Catalyst 3 is DMAP.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109232401A (en) * | 2018-11-13 | 2019-01-18 | 湖南比德生化科技股份有限公司 | A kind of method of trichlopyr ester distillation residual liquid recycling treatment |
| CN110317163A (en) * | 2019-07-18 | 2019-10-11 | 利尔化学股份有限公司 | The preparation method of Triclopyr butoxyethyl |
| CN113461604A (en) * | 2021-09-02 | 2021-10-01 | 潍坊新绿化工有限公司 | Method for preparing triclopyr butoxyethyl ester by aqueous phase synthesis method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010023679A2 (en) * | 2008-09-01 | 2010-03-04 | Excel Crop Care Limited | Preparation of triclopyr, its intermediate and butoxyethyl ester |
| CN102718700A (en) * | 2012-07-10 | 2012-10-10 | 南开大学 | Study on preparation and application of 3, 5, 6-trichlorine-2-pyridyloxyacetic acid derivatives |
| CN104672127A (en) * | 2015-02-10 | 2015-06-03 | 湖南比德生化科技有限公司 | Method for preparing 3, 5, 6-trichlopyr and salt thereof |
| CN105566211A (en) * | 2016-02-18 | 2016-05-11 | 江苏丰山集团股份有限公司 | Triclopyr production method |
-
2017
- 2017-07-08 CN CN201710553633.9A patent/CN107325044A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010023679A2 (en) * | 2008-09-01 | 2010-03-04 | Excel Crop Care Limited | Preparation of triclopyr, its intermediate and butoxyethyl ester |
| CN102718700A (en) * | 2012-07-10 | 2012-10-10 | 南开大学 | Study on preparation and application of 3, 5, 6-trichlorine-2-pyridyloxyacetic acid derivatives |
| CN104672127A (en) * | 2015-02-10 | 2015-06-03 | 湖南比德生化科技有限公司 | Method for preparing 3, 5, 6-trichlopyr and salt thereof |
| CN105566211A (en) * | 2016-02-18 | 2016-05-11 | 江苏丰山集团股份有限公司 | Triclopyr production method |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109232401A (en) * | 2018-11-13 | 2019-01-18 | 湖南比德生化科技股份有限公司 | A kind of method of trichlopyr ester distillation residual liquid recycling treatment |
| CN110317163A (en) * | 2019-07-18 | 2019-10-11 | 利尔化学股份有限公司 | The preparation method of Triclopyr butoxyethyl |
| CN113461604A (en) * | 2021-09-02 | 2021-10-01 | 潍坊新绿化工有限公司 | Method for preparing triclopyr butoxyethyl ester by aqueous phase synthesis method |
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Effective date of registration: 20180716 Address after: 438011 Guangming Road (Rudd Village), chemical industrial park, HuangZhou Railway Station, Huanggang, Hubei Applicant after: Wuhan Hua Bang chemical new material Co., Ltd. Address before: 300202 Xinian Square, Jiefang South Road, Hexi District, Tianjin 6-411 Applicant before: Yang Zihui |
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