CN108947824A - A kind of preparation method of phenoxy acetic acid ester - Google Patents
A kind of preparation method of phenoxy acetic acid ester Download PDFInfo
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- CN108947824A CN108947824A CN201810225346.XA CN201810225346A CN108947824A CN 108947824 A CN108947824 A CN 108947824A CN 201810225346 A CN201810225346 A CN 201810225346A CN 108947824 A CN108947824 A CN 108947824A
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- preparation
- acid ester
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- acetic acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
Abstract
The present invention provides a kind of preparation methods of phenoxy acetic acid ester, comprising the following steps: mixes phenolic compound in a solvent with chlorine carboxylate, acid binding agent, catalyst, one kettle way carries out condensation reaction, obtains benzene oxycarboxylic acid ester type compound；The solvent is one of DMF, DMSO, DMI and acetone or a variety of；The catalyst is quaternary ammonium salt or polyethylene glycol.The present invention realizes anhydrous synthesis phenoxy acetic acid ester, anhydrous output, and anhydrous participation is truly realized no effuent discharge, reduce the discharge amount of waste water, the later period is filtered to remove salt, without dehydration, energy consumption is lower, and the method for one kettle way makes reaction process simple, and equipment investment is few.And it reduces in later period ester hydrolysis reaction, ɑ-chlorinated carboxylic acid hydrolysis, to reduce the consumption of ɑ-chlorinated carboxylic acid, simultaneously effectively prevent the prior art because chloro phenoxy acetic acid sterling separation of solid and liquid caused by effective component loss, improve the yield of effective component, product purity height, high income.
Description
Technical field
The present invention relates to herbicide preparation technical field more particularly to a kind of preparation methods of phenoxy acetic acid ester, more have
Body, it is related to a kind of method of one pot process phenoxy acetic acid ester.
Background technique
Chlorine phenoxy carboxylic acid herbicides is the hormone-type selective herbicide of first kind merchandized handling in the world, to environment
Close friend has the characteristics that residual life is short and less toxic to people and other biological, seldom generates drug resistance, be mainly used for corn, wheat
Prevent and kill off broadleaf weed, nutgrass flatsedge and certain malignant weeds in equal gramineous crops field.
Widely used in chlorine phenoxy carboxylic acid herbicides is 2,4-D.Molecular formula is C8H6Cl2O3, fusing point 140.5
DEG C, 160 DEG C of boiling point, pure 2,4-D can exist in the form of sheet, powdery, crystal powder and solid etc., white slightly sepia,
The slightly smell of phenol, it is non-hygroscopic, it is corrosive.Solubility at 25 DEG C in water is 620mg/L, and it is big to dissolve in alcohol, ether, ketone etc.
Most organic solvents.Formula a is 2,4-D structural formula.
Industrially producing such product mainly has etherificate and first etherificate two main road Wiring technology of afterchlorinate after first chlorination.But two
Kind technique includes the process that phenol or chlorophenol and monoxone condensation prepare phenoxy acetic acid ester or chloro phenoxy acetic acid ester, should
Step needs carry out in water phase, and phenol and monoxone can all consume a large amount of liquid alkaline, cause later period waste water and abraum salt amount big, are processed into
This height, effect on environment is very big, has seriously affected the production and application of chlorine phenoxy carboxylic acid compound.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that provide a kind of preparation method of phenoxy acetic acid ester, one pot
Method synthesizes phenoxy acetic acid ester, substantially reduces wastewater flow rate, energy conservation and environmental protection.
In order to solve the above technical problems, the present invention provides a kind of preparation methods of phenoxy acetic acid ester, comprising the following steps:
Phenolic compound is mixed in a solvent with chlorine carboxylate, acid binding agent, catalyst, one kettle way carries out condensation reaction,
Obtain benzene oxycarboxylic acid ester type compound；
The solvent is one of DMF, DMSO, DMI and acetone or a variety of；
The catalyst is quaternary ammonium salt or polyethylene glycol.
Condensation reaction system of the invention is anhydrous system, has prevented the generation of high-salt wastewater.
The phenolic compound that the present invention uses is preferably phenol, o-cresol or chlorophenol etc..
The chlorine carboxylate has structure shown in formula I:
Wherein, R1The preferably alkylidene of C1~C5, the more preferably alkylidene of C1~C3, it is further, preferably sub-
Methyl (- CH2), methylmethylene (- CH (CH3) -), ethylidene (- CH2-CH2), propylidene (- CH2-CH2-CH2) or Aden
Base (- (CH2)4-)。
R is preferably the alkyl of C1~C10 or the naphthenic base of C3~C10, more preferably the alkyl of C1~C8 or C3~C8
Naphthenic base, it is further preferred that it is methyl, ethyl, propyl, isopropyl, normal-butyl, isobutyl group, iso-octyl or cyclohexyl.
In some embodiments of the invention, the chlorinated carboxylic acid ester is chloracetate.
The acid binding agent is preferably one of sodium carbonate, potassium carbonate and cesium carbonate or a variety of.
The catalyst is quaternary ammonium salt, preferably benzyltriethylammoinium chloride (TEBA), tetrabutylammonium bromide (TBAB), four
Butyl ammonium chloride, 4-butyl ammonium hydrogen sulfate, tri-n-octyl methyl ammonium chloride, dodecyl trimethyl ammonium chloride and tetradecyl trimethyl
One of ammonium chloride is a variety of.
The solvent is N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), 1,3- dimethyl -2- imidazoline
One of ketone (DMI) and acetone are a variety of, preferably DMF.
The present invention is to the source of above compound and is not particularly limited, and can be general commercially available.
The present invention uses special catalyst, and phenolic compound and chlorine carboxylate is enable to carry out in specific organic solvent
Condensation reaction, as long as above-mentioned preparation process disposably puts into phenolic compound, chlorine carboxylate, acid binding agent, catalysts and solvents
It can one kettle way preparation in reactor.
The mass ratio of the phenolic compound and solvent, acid binding agent, catalyst is preferably 1:(1.5~5): (1.02~2):
(0.1%~1%).
The chlorine carboxylate can be according to metering than addition, and the present invention is simultaneously not particularly limited.
The temperature of the condensation reaction is preferably 40~160 DEG C, and the reaction time is preferably 1~for 24 hours.
After above-mentioned condensation reaction, benzene oxycarboxylic acid ester type compound and bicarbonate are obtained, currently preferred, filtering
Desalination, filtrate separate solvent and benzene oxycarboxylic acid ester type compound through rectifying.
Compared with prior art, the present invention provides a kind of preparation methods of phenoxy acetic acid ester, comprising the following steps: by phenol
Class compound mixes in a solvent with chlorine carboxylate, acid binding agent, catalyst, and one kettle way carries out condensation reaction, obtains benzene oxycarboxylic acid
Ester type compound；The solvent is one of DMF, DMSO, DMI and acetone or a variety of；The catalyst is quaternary ammonium salt or gathers
Ethylene glycol.The present invention realizes anhydrous synthesis phenoxy acetic acid ester, the anhydrous output of whole process, and it is useless to be truly realized zero for anhydrous participation
Water discharge, greatly reduces the discharge amount of waste water, and the later period is filtered to remove salt, and without dehydration, energy consumption is lower, the side of one kettle way
Method makes reaction process simple, and equipment investment is few.And it reduces in later period ester hydrolysis reaction, ɑ-chlorinated carboxylic acid hydrolysis, thus
The consumption of ɑ-chlorinated carboxylic acid is reduced, while effectively preventing the prior art because the separation of solid and liquid of chloro phenoxy acetic acid sterling causes
Effective component loss, improve the yield of effective component, product purity is high, high income.
Specific embodiment
In order to further illustrate the present invention, below with reference to embodiment to the preparation method of phenoxy acetic acid ester provided by the invention
It is described in detail.
Embodiment 1
By phenol 95.1g (1mol), DMF 190g, tetrabutylammonium bromide 0.25g, methyl chloroacetate 109.6g
(1.00mol), potassium carbonate solid-state 140.8g (1.01mol) are mixed, and are warming up to 140 DEG C or so, react 10 hours.It cools to
Room temperature is filtered to remove potassium chloride and saleratus salt-mixture.Filter cake is washed twice with new 30g DMF, and filtrate and cleaning solution are mixed
Rectifying precipitation obtains product 160.5g, content 99.2%, yield 95.8% to constant weight.
It is generated in production process without waste water.
Embodiment 2
By phenol 95.1g (1mol), DMSO 190g, tetrabutylammonium bromide 0.25g, methyl chloroacetate 109.6g
(1.00mol), potassium carbonate solid-state 140.8g (1.01mol) are mixed, and are warming up to 150 DEG C or so, react 10 hours.It cools to
Room temperature is filtered to remove potassium chloride and saleratus salt-mixture.Filter cake is washed twice with new 30gDMF, and filtrate and cleaning solution are mixed
Rectifying precipitation obtains product 163.5g, content 99.1%, yield 96.6% to constant weight.
It is generated in production process without waste water.
Embodiment 3
By phenol 95.1g (1mol), acetone 200g, tetrabutylammonium bromide 0.25g, methyl chloroacetate 119.9g
(1.1mol), potassium carbonate solid-state 140.8g (1.01mol) are mixed, and are warming up to 60 DEG C or so, react 18 hours.Cool to room
Temperature is filtered to remove potassium chloride and saleratus salt-mixture.Filter cake twice, filtrate and cleaning solution is mixed de- with new 30g acetone washing
It is molten to constant weight, obtain product 158.1g, content 99.3%, yield 94.2%.
It is generated in production process without waste water.
Embodiment 4
By phenol 95.1g (1mol), DMF 190g, polyethylene glycol 0.5g, methyl chloroacetate 119.9g (1.1mol), carbonic acid
Potassium solid-state 140.8g (1.01mol) is mixed, and is warming up to 150 DEG C or so, reacts 10 hours.It cools to room temperature and is filtered to remove chlorine
Change potassium and saleratus salt-mixture.Filter cake is washed twice with new 30g DMF, by filtrate and cleaning solution mixing rectifying precipitation to perseverance
Weight, obtains product 165.5g, content 99.2%, yield 97.6%.
It is generated in production process without waste water.
Embodiment 5
By phenol 95.1g (1mol), DMF 190g, tetrabutylammonium bromide 0.25g, methyl chloroacetate 119.9g
(1.1mol), potassium carbonate solid-state 140.8g (1.01mol) are mixed, and are warming up to 150 DEG C or so, react 10 hours.It cools to
Room temperature is filtered to remove potassium chloride and saleratus salt-mixture.Filter cake is washed twice with new 30g DMF, and filtrate and cleaning solution are mixed
Rectifying precipitation obtains product 166.5g, content 99.1%, yield 97.2% to constant weight.
It is generated in production process without waste water.
Comparative example 1
Phenol 95.1g (1mol), liquid alkaline 125g (1mol32%) are first configured to sodium phenolate solution, then by 133g
(1.4mol) monoxone, 133g water, 175g liquid alkaline (1.4mol) are configured to neutralize material.Then heating sodium phenolate solution to 105 DEG C drip
Add neutralization to expect, later period control pH is added dropwise between 9 to 10, liquid alkaline consumes 15.2g at this time, and acidification is separated by filtration baking after condensation
Dry obtained phenoxy acetic acid 165.1g, content 98.7%, this step yield 97.6%.505g high-salt wastewater has been generated at this time.
Then 166.1g phenoxy acetic acid is obtained into methyl phenoxyacetate, esterification yield 97.3%, waste water with methanol esterification again
18g。
Two step total recoverys 94.96%；Total wastewater flow rate reaches 523g.Therefore prior art yield and a point water can not show a candle to the present invention
The one-step method of offer.
Comparative example 2
By phenol 95.1g (1mol), toluene 190g, tetrabutylammonium bromide 0.25g, methyl chloroacetate 119.9g
(1.1mol), potassium carbonate solid-state 140.8g (1.01mol) are mixed, and are warming up to 110 DEG C or so, react 10 hours.It cools to
Room temperature is filtered to remove potassium chloride and saleratus salt-mixture.Filter cake is washed twice with new 30g toluene, and filtrate and cleaning solution are mixed
Rectifying precipitation obtains product 22.5g, content 91.1%, yield 12.1% to constant weight.
Comparative example 3
By phenol 95.1g (1mol), DMF 190g, methyl chloroacetate 119.9g (1.1mol), potassium carbonate solid-state 140.8g
(1.01mol) is mixed, and is warming up to 150 DEG C or so, reacts 10 hours.It cools to room temperature and is filtered to remove potassium chloride and bicarbonate
Potassium salt-mixture.Filter cake is washed twice with new 30g DMF, by filtrate and cleaning solution mixing rectifying precipitation to constant weight, obtains product
112.1g, content 96.1%, yield 64.8%.
By above-described embodiment and comparative example it is found that preparation method provided by the invention, realizes one kettle way preparation, and without useless
Water generates.
The above description of the embodiment is only used to help understand the method for the present invention and its core ideas.It should be pointed out that pair
For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out
Some improvements and modifications, these improvements and modifications also fall within the scope of protection of the claims of the present invention.
Claims (8)
1. a kind of preparation method of phenoxy acetic acid ester, comprising the following steps:
Phenolic compound is mixed in a solvent with chlorine carboxylate, acid binding agent, catalyst, one kettle way carries out condensation reaction, obtains
Benzene oxycarboxylic acid ester type compound；
The solvent is one of DMF, DMSO, DMI and acetone or a variety of；
The catalyst is quaternary ammonium salt or polyethylene glycol.
2. preparation method according to claim 1, which is characterized in that the phenolic compound is phenol, o-cresol or chlorine
Substituting phenol.
3. preparation method according to claim 1, which is characterized in that the chlorine carboxylate has structure shown in formula I:
Wherein,
R1For the alkylidene of C1~C5；
R is the alkyl of C1~C10 or the naphthenic base of C3~C10.
4. preparation method according to claim 1, which is characterized in that the acid binding agent is sodium carbonate, potassium carbonate and carbonic acid
One of caesium is a variety of.
5. preparation method according to claim 1, which is characterized in that the catalyst is benzyltriethylammoinium chloride, four
Butylammonium bromide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate, tri-n-octyl methyl ammonium chloride, dodecyl trimethyl ammonium chloride
With one of tetradecyl trimethyl ammonium chloride or a variety of.
6. preparation method according to claim 1, which is characterized in that the phenolic compound and solvent, acid binding agent, catalysis
The mass ratio of agent is 1:(1.5~5): (1.02~2): (0.1%~1%).
7. preparation method according to claim 1, which is characterized in that the temperature of the condensation reaction is 40~160 DEG C, instead
Between seasonable for 1~for 24 hours.
8. preparation method according to claim 1, which is characterized in that after the condensation reaction, filter desalination, filtrate
Through rectifying, solvent and benzene oxycarboxylic acid ester type compound are separated.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810225346.XA CN108947824A (en) | 2018-03-19 | 2018-03-19 | A kind of preparation method of phenoxy acetic acid ester |
| PCT/CN2019/076256 WO2019179286A2 (en) | 2018-03-19 | 2019-02-27 | Preparation method for phenoxyacetate |
| ARP190100682A AR115275A1 (en) | 2018-03-19 | 2019-03-19 | METHOD FOR PREPARING PHENOXY ACETATE |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810225346.XA CN108947824A (en) | 2018-03-19 | 2018-03-19 | A kind of preparation method of phenoxy acetic acid ester |
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| Publication Number | Publication Date |
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| CN108947824A true CN108947824A (en) | 2018-12-07 |
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| CN201810225346.XA Withdrawn CN108947824A (en) | 2018-03-19 | 2018-03-19 | A kind of preparation method of phenoxy acetic acid ester |
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|---|---|
| CN (1) | CN108947824A (en) |
| AR (1) | AR115275A1 (en) |
| WO (1) | WO2019179286A2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110028406A (en) * | 2019-05-22 | 2019-07-19 | 鹤岗市英力农化有限公司 | A kind of synthetic method of substituted phenoxy acetic acid ester type compound |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106242971A (en) * | 2016-08-04 | 2016-12-21 | 山东省化工研究院 | A kind of chloracetate synthesis in water technology and the new method of preparation 2,4 D esters thereof |
-
2018
- 2018-03-19 CN CN201810225346.XA patent/CN108947824A/en not_active Withdrawn
-
2019
- 2019-02-27 WO PCT/CN2019/076256 patent/WO2019179286A2/en active Application Filing
- 2019-03-19 AR ARP190100682A patent/AR115275A1/en unknown
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106242971A (en) * | 2016-08-04 | 2016-12-21 | 山东省化工研究院 | A kind of chloracetate synthesis in water technology and the new method of preparation 2,4 D esters thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110028406A (en) * | 2019-05-22 | 2019-07-19 | 鹤岗市英力农化有限公司 | A kind of synthetic method of substituted phenoxy acetic acid ester type compound |
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| Publication number | Publication date |
|---|---|
| WO2019179286A2 (en) | 2019-09-26 |
| AR115275A1 (en) | 2020-12-16 |
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