CN108947822A - A kind of preparation method of phenoxy carboxylic acid herbicides - Google Patents
A kind of preparation method of phenoxy carboxylic acid herbicides Download PDFInfo
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- CN108947822A CN108947822A CN201810226592.7A CN201810226592A CN108947822A CN 108947822 A CN108947822 A CN 108947822A CN 201810226592 A CN201810226592 A CN 201810226592A CN 108947822 A CN108947822 A CN 108947822A
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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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
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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
- C07C67/307—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 halogen; by substitution of halogen atoms by other halogen atoms
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Abstract
The present invention provides a kind of preparation methods of phenoxy carboxylic acid herbicides, comprising: S1, by phenol or o-cresol under alkaline matter effect, carry out condensation reaction with chlorinated carboxylic acid ester, obtain benzene oxycarboxylic acid ester；The chlorinated carboxylic acid ester general formula is ClR1COOR, R1For the alkylidene or alkylidene of C1~3, R is the alkyl of C1~10 or the naphthenic base of C3~10；S2, by the benzene oxycarboxylic acid ester under the first catalyst and the second catalyst action, with chlorinating agent carry out selective chlorination, obtain chlorobenzene oxycarboxylic acid ester；First catalyst is selected from lewis acid, and the second catalyst is thio-ether type compounds, thiazole compound, different thiazoles compound or the thiophenes of C5~22；S3, the chlorobenzene oxycarboxylic acid ester is subjected to acidolysis reaction, obtains phenoxy carboxylic acid herbicides shown in Formulas I, R3For H, Cl or CH3.The present invention can improve the operating environment of product quality and production scene, and the three wastes are few.
Description
Technical field
The present invention relates to technical field of organic synthesis, more particularly, to a kind of preparation method of phenoxy carboxylic acid herbicides.
Background technique
Phenoxy carboxylic acid herbicides is a kind of important herbicide, due to its weeding fast speed, herbicidal spectrum is wider the advantages that,
Agriculturally it is being widely used.The necessary condition of phenoxy carboxylic acid reactive compound structure includes: a phenyl ring, an oxygen original on ring
Son replaces；The aliphatic chain being connected with oxygen atom and a carboxyl；Contain different substituent groups on phenyl ring, wherein taking with the 2nd, 4
The compound activity highest in generation.Due to the architectural difference of the groups such as benzene ring substitution group, different herbicide kinds can be formed；Agricultural
The more acid and esters for having such herbicide is used in production.This kind of herbicide includes the benzene oxygen carboxylic for having following structure general formula
Acid compounds:
In formula a, R1The alkylidene or alkylidene for being 1~3 for carbon atom number, R2For H, carbon atom number be 3~10 alkyl or
Naphthenic base, R3For H, Cl or CH3。
The existing above-mentioned phenoxy carboxylic acid herbicides (R being generally used2Preparation method for H) mainly has following two
Step: (1) using phenol as primary raw material, chlorinated phenol is made through chlorination；(2) chlorinated phenol contracts with chlorinated carboxylic acid under alkaline condition
Reaction is closed, gained reaction solution is acidified, filters, and obtains acids in phenoxy carboxylic acid herbicides wet feed, benzene oxygen carboxylic is obtained after drying
Acid herbicides.
In the above method, the chlorinated phenol of (1) step output has the penetrating odor of extremely difficult news, leads to production on-site environment
It is very poor, and chlorination is selectively poor.And in (2) step, it is intermolecular that Dichlorophenol or multi-chlorophenol in chlorinated phenol can occur two
Condensation can not only generate to generate hypertoxicity substance-dioxin of extremely difficult degradation and largely contain chlorinated phenol, chlorobenzene oxygen carboxylic
The dangerous waste of acid, and also contains dioxin in the phenoxy carboxylic acid herbicides product of output, this is strong to environment and producers'
Health brings great risk, and product quality is poor.In addition, dioxin can also be with phenoxy carboxylic acid herbicides and its derived product
Use enter plant, air, soil and water source, and as food chain is enriched with, in turn result in more serious environment and strong
Health harm.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that providing a kind of preparation side of phenoxy carboxylic acid herbicides
Method, this method can improve the operating environment of product quality and production scene.
The present invention provides a kind of preparation method of phenoxy carboxylic acid herbicides, comprising the following steps:
S1, by phenol or o-cresol in the presence of alkaline substances, carry out condensation reaction with chlorinated carboxylic acid ester, obtain
Benzene oxycarboxylic acid ester；
The general formula of the chlorinated carboxylic acid ester is ClR1COOR, wherein R1The alkylidene or secondary alkane for being 1~3 selected from carbon atom number
Base, R are selected from the alkyl that carbon atom number is 1~10 or the naphthenic base that carbon atom number is 3~10；
S2, by the benzene oxycarboxylic acid ester existing for the first catalyst and the second catalyst under the conditions of, carried out with chlorinating agent
Selective chlorination obtains chlorobenzene oxycarboxylic acid ester；First catalyst is selected from lewis acid, and second catalyst is selected from carbon
Thiazole compound that thio-ether type compounds that atomicity is 5~22, carbon atom number are 5~22, carbon atom number be 5~22 it is different
The thiophenes that thiazole compound or carbon atom number are 5~22；
S3, the chlorobenzene oxycarboxylic acid ester is subjected to acidolysis reaction, obtains phenoxy carboxylic acid herbicides shown in Formulas I；
In Formulas I, R1The alkylidene or alkylidene for being 1~3 selected from carbon atom number, R3For H, Cl or CH3。
Preferably, in S1 step, the alkaline matter is sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, carbon
Sour hydrogen sodium, saleratus, sodium carbonate or potassium carbonate.
Preferably, in S1 step, the alkaline matter is sodium hydroxide, potassium hydroxide, sodium bicarbonate or saleratus, institute
The molar ratio for stating phenol or o-cresol and alkaline matter is 1:(1~1.08)；
Alternatively, the alkaline matter is calcium hydroxide, magnesium hydroxide, sodium carbonate or potassium carbonate, the phenol or o-cresol
Molar ratio with alkaline matter is 1:(0.5~0.54).
Preferably, in S1 step, the condensation reaction carries out in organic solvent, the organic solvent be benzene, toluene or
Dimethylbenzene.
Preferably, in S1 step, the dosage of the organic solvent is 1~5 times of phenol or o-cresol weight.
Preferably, in S1 step, the molar ratio of the phenol or o-cresol and chlorinated carboxylic acid ester is 1:(1~1.08), institute
The temperature for stating condensation reaction is 60~120 DEG C.
Preferably, in S2 step, the chlorinating agent is chlorine, thionyl chloride or chlorosulfuric acid.
Preferably, in S2 step, the molar ratio of the benzene oxycarboxylic acid ester and chlorinating agent is 1:(1.98~2.4), S3 step
Middle R3For Cl；
Alternatively, the molar ratio of the benzene oxycarboxylic acid ester and chlorinating agent is 1:(0.99~1.2), R in S3 step3For H or CH3。
Preferably, in S2 step, the dosage of first catalyst is the 0.05%~1.0% of benzene oxycarboxylic acid ester weight,
The dosage of second catalyst is the 0.05%~1.0% of benzene oxycarboxylic acid ester weight.
Preferably, in S2 step, the temperature of the selective chlorination reaction is -20~100 DEG C.
The present invention synthesizes benzene oxycarboxylic acid ester through condensation using phenol, and then selective chlorination synthesizes chlorobenzene oxycarboxylic acid ester, most
Acidolysis synthesizes phenoxy carboxylic acid herbicides afterwards.Compared with existing synthetic technology, the present invention is effectively avoided with bad smell
Chlorinated phenol production and use, fundamentally prevented severe toxicity dioxin generation, greatly improve product quality and
The operating environment of production scene.Experiment display, gained phenoxy carboxylic acid herbicides product content >=98.5%, total recovery >=
98%.The present invention, through condensation, selective chlorination and acidolysis, has obtained the phenoxy carboxylic acid herbicides of high-quality using phenol as raw material,
Method of the invention efficiently avoids the loss of effective component, improves the yield of product.
In addition, the present invention by the innovation to process route, has effectively prevented the generation of high COD, high-salt wastewater, give up simultaneously
The quantum of output of salt (metal chloride) reduces 50% or more, and three wastes output has pole significantly to reduce, three-protection design cost
It declines to a great extent.
Detailed description of the invention
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of 1 gained 2,4 dichlorophenoxyacetic acid of the embodiment of the present invention.
Specific embodiment
The present invention provides a kind of preparation methods of phenoxy carboxylic acid herbicides, comprising the following steps:
S1, by phenol or o-cresol in the presence of alkaline substances, carry out condensation reaction with chlorinated carboxylic acid ester, obtain
Benzene oxycarboxylic acid ester；
The general formula of the chlorinated carboxylic acid ester is ClR1COOR, wherein R1The alkylidene or secondary alkane for being 1~3 selected from carbon atom number
Base, R are selected from the alkyl that carbon atom number is 1~10 or the naphthenic base that carbon atom number is 3~10；
S2, by the benzene oxycarboxylic acid ester existing for the first catalyst and the second catalyst under the conditions of, carried out with chlorinating agent
Selective chlorination obtains chlorobenzene oxycarboxylic acid ester；First catalyst is selected from lewis acid, and second catalyst is selected from carbon
Thiazole compound that thio-ether type compounds that atomicity is 5~22, carbon atom number are 5~22, carbon atom number be 5~22 it is different
The thiophenes that thiazole compound or carbon atom number are 5~22；
S3, the chlorobenzene oxycarboxylic acid ester is subjected to acidolysis reaction, obtains phenoxy carboxylic acid herbicides shown in Formulas I；
In Formulas I, R1The alkylidene or alkylidene for being 1~3 selected from carbon atom number, R3For H, Cl or CH3。
The preparation method of phenoxy carboxylic acid herbicides provided by the invention can improve the operating environment of production scene, and have
Have the advantages that superior product quality, high income, the three wastes are few.
The embodiment of the present invention puts into a certain proportion of alkaline matter, under certain temperature using phenol as primary raw material thereto
Chlorinated carboxylic acid ester is added to be allowed to react, obtains benzene oxycarboxylic acid ester.Wherein, phenol of the present invention refers to phenol or o-cresol.
The general formula of chlorinated carboxylic acid ester of the present invention is ClR1COOR, R in formula1The alkylidene for being 1~3 selected from carbon atom number
Or alkylidene, specifically, R1=CH2、CH(CH3) or (CH2)3.R is selected from the alkyl that carbon atom number is 1~10 or carbon atom number is 3
~10 naphthenic base is preferably selected from the alkyl that carbon atom number is 1~4.In an embodiment of the present invention, the chlorinated carboxylic acid ester is
Methyl chloroacetate, ethyl chloroacetate, isopropyl chloracetate, Solid acid n-butyl chloroacete, iso-butyl chloroacetate, Isooctyl chloroacetate, chlorine
The positive last of the ten Heavenly stems ester of n-butyl propionate, chloropropionic acid, neoprene acid ethyl ester or the different monooctyl ester of chloro-butyric acid.
The present invention uses above-mentioned phenol and chlorinated carboxylic acid ester ClR1COOR synthesizes benzene oxycarboxylic acid ester, the benzene oxygen carboxylic through condensation
Acid esters refers to the substance having following structure:
The present invention carries out condensation reaction in the presence of alkaline substances, obtains chloride and benzene oxycarboxylic acid ester；It is described
Alkaline matter be preferably sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, sodium bicarbonate, saleratus, sodium carbonate or
Potassium carbonate.
In some embodiments of the invention, the condensation reaction can carry out in organic solvent, and reaction system is opposite
Uniformly；The organic solvent is preferably benzene, toluene or dimethylbenzene.The embodiment of the present invention puts into a certain proportion of alkali into phenol and has
Solvent, temperature rising reflux are dehydrated to biodiversity content≤0.5%, and chlorinated carboxylic acid ester is added dropwise thereto under certain temperature,
Insulation reaction 0.5h, cooling filtering at a temperature of this after being added dropwise, and suitable above-mentioned solvent is added, wash filter cake, drying
Metal chloride and the benzene oxycarboxylic acid ester crude product containing solvent, retortable recycling design are obtained, while obtaining the production of benzene oxycarboxylic acid ester
Object.
Wherein, when the alkaline matter is sodium hydroxide, potassium hydroxide, sodium bicarbonate or saleratus, phenol and alkalinity
The molar ratio of substance can be 1:(1~1.08), preferred 1:(1~1.04), more preferable 1:(1.02~1.04)；When the basic species
Matter is calcium hydroxide, magnesium hydroxide, sodium carbonate or potassium carbonate, and the molar ratio of phenol and alkaline matter can be 1:(0.5~0.54), it is excellent
Select 1:(0.5~0.52), more preferable 1:(0.51~0.52).In reaction process, the dosage of the organic solvent is generally phenol weight
1~5 times, preferably 1.5~2.5 times of amount.
In the present invention, the molar ratio of phenol and chlorinated carboxylic acid ester can be 1:(1~1.08), preferred 1:(1~1.04), more excellent
Select 1:(1.02~1.04).The temperature of the condensation reaction can be 60~120 DEG C, preferably 60~100 DEG C, more preferable 80~100
℃.Gained condensation liquid is filtered and conventional wash and dries to obtain crude product；Wherein filtration temperature is generally 30~50 DEG C.
After obtaining benzene oxycarboxylic acid ester, a certain proportion of first catalyst and the second catalysis is added in the embodiment of the present invention thereto
Then a certain amount of chlorinating agent is added under certain temperature and carries out selective chlorination reaction for agent, addition finishes insulation reaction 0.5h,
Obtain chlorobenzene oxycarboxylic acid ester.
In the present invention, first catalyst is lewis acid.The substance of a usually acceptable electronics pair is exactly road
Lewis acid；Lewis acid catalyst of the present invention generally uses: (1) containing the chloride of Mg, Fe, Al, Zn, Ti or Sn；(2) contain
The oxide of Mg, Fe, Al, Zn, Ti or Sn；(3) fluoride, such as BF3、SbF5Deng；(4) phenylacetic acid compound, such as Pb (OAc)2、
Zn(OAc)2Deng.Specifically, first catalyst includes but are not limited to SnCl4、MgCl2、FeCl3、AlCl3、ZnCl2、
TiCl4、BF3、SbF5、Al2O3、Fe2O3、TiO2、Pb(OAc)2、Zn(OAc)2Or Al2O(OAc)4, preferably MgCl2、FeCl3、
ZnCl2、SbF5、TiO2、Pb(OAc)2, more preferably FeCl3、TiO2、Pb(OAc)2。
In the present invention, second catalyst be carbon atom number be 5~22 thio-ether type compounds, carbon atom number 5
The thiophene-based that the different thiazoles compound or carbon atom number that~22 thiazole compound, carbon atom number are 5~22 are 5~22
Thioether, thiazole, isothiazole, thiophene or their halo derivatives that conjunction object, preferably carbon atom number are 5~22, including but not
It is only limitted to tertbutyl methyl thioether, tert-butylsulfide, diphenyl sulfide, 4,4'- dichloro diphenyl sulfide, 2- methyl diphenyl sulfide, 2,4,6- tri-
Methyl diphenyl sulfide, 4,4'- thiobis (6- tert-butyl -3- methylphenol), thiazole, 2- ethyl thiazole, 2,5- dichloro thiazole, 4- first
Base thiazole, 2- tertiary butyl thiazole, isothiazole, 4,5- dimethyl isothiazole, 5- chloroisothiazole, 2,4,5- tri-tert isothiazole,
Thiophene, 2- methylthiophene, 2,5- thioxene, 3- chlorothiophene, 3,4- dichloro-thiophene, 2,3,4- tri- chlorothiophenes, wherein it is preferred that
Tert-butylsulfide, 2,4,6- trimethylbenzene thioether, 4,4'- thiobis (6- tert-butyl -3- methylphenol), 2- ethyl thiazole, 2,
5- dichloro thiazole, 2,4,5- tri-tert isothiazole, 4,5- dimethyl isothiazole, 3,4- dichloro-thiophene, 2,3,4- tri- chlorothiophenes,
More preferable tert-butylsulfide, 4,4'- thiobis (6- tert-butyl -3- methylphenol), 2,4,5- tri-tert isothiazole, 2,3,4-
Three chlorothiophenes.
In an embodiment of the present invention, first catalyst and/or the second catalyst can also be deposited in the form of load
In as loaded catalyst；Preferred catalyst carrier is silica gel (main component is silica), and catalyst passes through dipping
Method is loaded in catalyst carrier.The load factor of first catalyst and the second catalyst is respectively 10%~20%, 5%~
15%.
In the present invention, partially using be separated by distillation in the embodiment of unsupported catalyst catalyst and product from
And obtain chlorobenzene oxycarboxylic acid ester；It, can be with and in the embodiment that the first catalyst of part and the second catalyst are support type
It is not required to distillation and directly realizes the separation of catalyst and chlorobenzene oxycarboxylic acid ester by filtering, particularly, when by the first catalyst
When being fixed in reactor with the second catalyst, in this embodiment it is not even necessary to filtering can isolated chlorobenzene oxycarboxylic acid ester, this makes
The separation of catalyst and product becomes simple and easy, while improving the service efficiency of catalyst, saves a large amount of energy consumptions, and
It is particularly suitable for carrying out continuous operation.
In an embodiment of the present invention, the dosage of first catalyst can for benzene oxycarboxylic acid ester weight 0.05%~
1.0%, preferably 0.25%~1.0%, more preferably 0.5%~1.0%.The dosage of second catalyst can be benzene oxygen carboxylic
The 0.05%~1.0% of acid esters weight, preferably 0.2%~0.8%, more preferably 0.3%~0.5%.When the first catalyst
In the presence of in the form of loaded catalyst, the dosage of effective component is benzene oxycarboxylic acid ester weight in loaded catalyst
0.05%~1.0%, preferably 0.25%~1.0%, more preferably 0.5%~1.0%, having in loaded catalyst herein
Effect ingredient refers to the first catalyst being carried on carrier, the first catalyst of effective ingredient consumption=support type of the first catalyst
Usage amount × load factor.In the presence of the second catalyst is in the form of loaded catalyst, in loaded catalyst effectively at
Point dosage be benzene oxycarboxylic acid ester weight 0.05%~1.0%, preferably 0.2%~0.8%, more preferably 0.3%~
0.5%, the effective component in loaded catalyst refers to that the second catalyst being carried on carrier, the second catalyst have herein
Imitate usage amount × load factor of the second catalyst of Ingredient Amount=support type.
Chlorinating agent of the present invention is preferably chlorine, thionyl chloride or chlorosulfuric acid, more preferably chlorine or chlorosulfuric acid.This hair
The bright selective chlorination on the phenyl ring of synthesized benzene oxycarboxylic acid ester, obtains chlorobenzene oxycarboxylic acid ester.Selectivity of the present invention
Chlorination reaction temperature can be -20~100 DEG C, preferably -20~60 DEG C, more preferably -20~20 DEG C.Chlorobenzene oxygen carboxylic of the present invention
Acid esters refers to the substance having following structure:
The molar ratio of benzene oxycarboxylic acid ester and chlorinating agent of the present invention can be by following selection: when benzene oxycarboxylic acid ester is Formula II -1
And target product is when being -2 formula of formula III, is 1:(1.98~2.4 with the molar ratio of chlorinating agent), preferred 1:(2~2.2), more excellent
Select 1:(2.02~2.06)；Molar ratio when benzene oxycarboxylic acid ester is Formula II -1 and target product is formula III -1, with chlorinating agent
For 1:(0.99~1.2), preferred 1:(1~1.1), more preferable 1:(1.01~1.03)；When benzene oxycarboxylic acid ester is Formula II -2,
It is 1:(0.99~1.2 with the molar ratio of chlorinating agent), preferred 1:(1~1.1), more preferable 1:(1.01~1.03).
Benzene oxycarboxylic acid ester selective chlorination in the embodiment of the present invention obtains chlorobenzene oxycarboxylic acid ester.Then, by the chloro
Benzene oxycarboxylic acid ester carries out acidolysis reaction, obtains phenoxy carboxylic acid herbicides shown in Formulas I.Also, generated hydrogen chloride can return
It receives and is used for benzene oxycarboxylic acid ester acidolysis reaction, directly obtain benzene oxycarboxylic acid and alcohol.
A certain amount of acid is added into the chlorinated carboxylic acid ester in the embodiment of the present invention, under certain temperature acidolysis reaction 2h~
4h, while the alcohol that reaction generates is steamed, it is cooled to room temperature after completion of the reaction, filters, and a small amount of water washing filter cake is added, filter cake dries
Do to obtain phenoxy carboxylic acid herbicides.
Acid of the present invention can be hydrochloric acid, phosphoric acid, sulfuric acid or sulfonic acid XSO3The sulfonic acid substances such as H, wherein X is that carbon is former
Alkyl, aryl, the alkyl or aryl that is optionally substituted by halogen of the subnumber for 1~18.In addition, acidolysis of the present invention preferably uses non-oxidation
Property, high boiling phosphoric acid soluble easily in water, sulfonic acid ensure that the recycling of product quality and catalyst as catalyst；Phase
Compared with technique of the solid acid as catalyst is used, reaction speed can not only be accelerated, can also reduce the separation of product and catalyst
Difficulty.
In an embodiment of the present invention, mass concentration sour used in the chlorobenzene oxycarboxylic acid ester acidolysis can for 5%~
35%；Hundred dosage of folding of acid is 0.4~1 times of chlorobenzene oxycarboxylic acid ester weight.In the present invention, the acidolysis reaction temperature can
It is 60~120 DEG C, preferably 80~100 DEG C.Phenoxy carboxylic acid herbicides obtained by acidolysis of the present invention have Formulas I structure, in particular to
Substance with formula:
Experiment display, gained phenoxy carboxylic acid herbicides product content >=98.5% of the embodiment of the present invention, total recovery >=
98%, washing water and filtrate merge reuse.Compared with prior art, method of the invention efficiently avoids the damage of effective component
It loses, improves the yield of product.It is each target product and impurity situation (mass content) in some embodiments of the invention below:
Each target product and impurity situation in 1 some embodiments of the invention of table
In conclusion the preparation method of phenoxy carboxylic acid herbicides provided by the invention avoids the production of chlorinated phenol and makes
With, can fundamentally prevent severe toxicity dioxin generation, significantly improve the environment of product quality and Workplace, mention simultaneously
In high yield.In addition, the present invention by the innovation to process route, has effectively prevented the generation of high COD, high-salt wastewater, give up simultaneously
The quantum of output of salt (metal chloride) reduces 50% or more, and three wastes output has pole significantly to reduce, three-protection design cost
It declines to a great extent, is conducive to industrialization promotion.
In order to further illustrate the present invention, with reference to embodiments to the system of phenoxy carboxylic acid herbicides provided by the invention
Preparation Method is described in detail.
In following embodiment, related raw material is commercially available.
Embodiment 1
Into the phenol of 95.06g purity 99%, the sodium hydroxide and 142.59g dimethylbenzene of 42.83g purity 99% is added,
Temperature rising reflux is dehydrated to moisture≤0.5%, and the methyl chloroacetate for being added dropwise to 116.20g purity 99% thereto at 90 DEG C is allowed to
Reaction, is added dropwise insulation reaction 0.5h at a temperature of this, is cooled to 40 DEG C, filters, and suitable dimethylbenzene washing filter is added
Cake dries to obtain sodium chloride and the methyl phenoxyacetate crude product containing dimethylbenzene later, is distilled to recover dimethylbenzene, while obtaining phenoxy acetic acid
Methyl esters 172.02g, content 96.1%.
Into distillation gained methyl phenoxyacetate, the tin tetrachloride and 0.60g purity 99% of 1.72g purity 99% is added
2,5- dichloro thiazoles, the chlorosulfuric acid that 279.41g purity 99% is added at 60 DEG C are allowed to react, and addition is finished to be protected at a temperature of this
Temperature reaction 0.5h, distills and is collected under 1kPa pressure 115~125 DEG C of fraction, obtain 2,4- dichlorphenoxyacetic acid methyl esters
234.12g content 99.18%.
To gained 2, the hydrochloric acid of 780.40g concentration 30% is added in 4- dichlorphenoxyacetic acid methyl esters, acidolysis is anti-at 110 DEG C
4h is answered, while steaming the alcohol that reaction generates, room temperature is cooled to after completion of the reaction, filters, and add a small amount of water washing filter cake, filter cake dries
It is dry, 2,4- dichlorphenoxyacetic acid 219.46g is obtained, structure detection spectrogram is referring to Fig. 1, Fig. 11HNMR (DMSO-d6) spectrogram；Contain
Amount 98.8%, total recovery in terms of phenol 98.0%.
Comparative example 1
Into the phenol of 95.06g purity 99%, the sodium hydroxide and 142.59g dimethylbenzene of 42.83g purity 99% is added,
Temperature rising reflux is dehydrated to moisture≤0.5%, and the methyl chloroacetate for being added dropwise to 116.20g purity 99% thereto at 90 DEG C is allowed to
Reaction, is added dropwise insulation reaction 0.5h at a temperature of this, is cooled to 40 DEG C, filters, and suitable dimethylbenzene washing filter is added
Cake dries to obtain sodium chloride and the methyl phenoxyacetate crude product containing dimethylbenzene later, is distilled to recover dimethylbenzene, while obtaining phenoxy acetic acid
Methyl esters 172.02g, content 96.1%.
Into distillation gained methyl phenoxyacetate, the tin tetrachloride of 1.72g purity 99% is added, is added at 60 DEG C
The chlorosulfuric acid of 279.41g purity 99% is allowed to react, and addition finishes insulation reaction 0.5h at a temperature of this, steams under 1kPa pressure
The fraction for evaporating and collecting 115~125 DEG C obtains 2,4- dichlorphenoxyacetic acid methyl esters 210.71g, content 99.03%.
To gained 2, the hydrochloric acid of 702.36g concentration 30% is added in 4- dichlorphenoxyacetic acid methyl esters, acidolysis is anti-at 110 DEG C
4h is answered, while steaming the alcohol that reaction generates, room temperature is cooled to after completion of the reaction, filters, and add a small amount of water washing filter cake, filter cake dries
It is dry, obtain 2,4- dichlorphenoxyacetic acid 197.34g, content 98.7%, total recovery in terms of phenol 88.0%.
Comparative example 2
Into the phenol of 95.06g purity 99%, the sodium hydroxide and 142.59g dimethylbenzene of 42.83g purity 99% is added,
Temperature rising reflux is dehydrated to moisture≤0.5%, and the methyl chloroacetate for being added dropwise to 116.20g purity 99% thereto at 90 DEG C is allowed to
Reaction, is added dropwise insulation reaction 0.5h at a temperature of this, is cooled to 40 DEG C, filters, and suitable dimethylbenzene washing filter is added
Cake dries to obtain sodium chloride and the methyl phenoxyacetate crude product containing dimethylbenzene later, is distilled to recover dimethylbenzene, while obtaining phenoxy acetic acid
Methyl esters 172.02g, content 96.1%.
Into distillation gained methyl phenoxyacetate, 2, the 5- dichloro thiazole of 0.60g purity 99% is added, is added at 60 DEG C
The chlorosulfuric acid of 279.41g purity 99% is allowed to react, and addition finishes insulation reaction 0.5h at a temperature of this, steams under 1kPa pressure
The fraction for evaporating and collecting 115~125 DEG C obtains 2,4- dichlorphenoxyacetic acid methyl esters 189.64g, content 98.89%.
To gained 2, the hydrochloric acid of 632.12g concentration 30% is added in 4- dichlorphenoxyacetic acid methyl esters, acidolysis is anti-at 110 DEG C
4h is answered, while steaming the alcohol that reaction generates, room temperature is cooled to after completion of the reaction, filters, and add a small amount of water washing filter cake, filter cake dries
It is dry, obtain 2,4- dichlorphenoxyacetic acid 179.28g, content 98.4%, total recovery in terms of phenol 79.18%.
Comparative example 3
Into the phenol of 95.06g purity 99%, the sodium hydroxide and 142.59g dimethylbenzene of 42.83g purity 99% is added,
Temperature rising reflux is dehydrated to moisture≤0.5%, and the methyl chloroacetate for being added dropwise to 116.20g purity 99% thereto at 90 DEG C is allowed to
Reaction, is added dropwise insulation reaction 0.5h at a temperature of this, is cooled to 40 DEG C, filters, and suitable dimethylbenzene washing filter is added
Cake dries to obtain sodium chloride and the methyl phenoxyacetate crude product containing dimethylbenzene later, is distilled to recover dimethylbenzene, while obtaining phenoxy acetic acid
Methyl esters 172.02g, content 96.1%.
The chlorosulfuric acid that 279.41g purity 99% is added into distillation gained methyl phenoxyacetate at 60 DEG C is allowed to react,
Addition finishes insulation reaction 0.5h at a temperature of this, and 115~125 DEG C of fraction is distilled and collected under 1kPa pressure, obtains 2,4-
Dichlorphenoxyacetic acid methyl esters 170.87g, content 98.76%.
To gained 2, the hydrochloric acid of 568.91g concentration 30% is added in 4- dichlorphenoxyacetic acid methyl esters, acidolysis is anti-at 110 DEG C
4h is answered, while steaming the alcohol that reaction generates, room temperature is cooled to after completion of the reaction, filters, and add a small amount of water washing filter cake, filter cake dries
It is dry, obtain 2,4- dichlorphenoxyacetic acid 159.87g, content 98.5%, total recovery in terms of phenol 71.24%.
Embodiment 2
Into the o-cresol of 109.23g purity 99%, the potassium carbonate and 109.23g toluene of 69.80g purity 99% is added,
Temperature rising reflux is dehydrated to moisture≤0.5%, is added dropwise to the Solid acid n-butyl chloroacete of 152.14g purity 99% thereto at 120 DEG C
It is allowed to react, insulation reaction 0.5h at a temperature of this is added dropwise, be cooled to 30 DEG C, filter, and suitable toluene washing is added
Filter cake dries to obtain potassium chloride and methylphenoxyacetic acid N-butyl crude product containing toluene later, is distilled to recover toluene, while obtaining adjacent
Methylphenoxyacetic acid N-butyl 230.89g, content 95.9%.
Into distillation gained methylphenoxyacetic acid N-butyl, iron chloride/silica gel load that 1.15g load factor is 10% is added
Tertbutyl methyl thioether/silica gel supported catalyst that type catalyst and 15.4g load factor are 15%, is added dropwise at 40 DEG C
The thionyl chloride of 118.46g purity 99% is allowed to react, and addition finishes insulation reaction 0.5h at a temperature of this, filters, it is chloro- to obtain 4-
2- methyl phenoxy acetic acid N-butyl 256.98g, content 99.01%.
The hydrochloric acid of 1370.55g concentration 15% is added into gained methoxone N-butyl, at 70 DEG C
Acidolysis reaction 4h, while the alcohol that reaction generates is steamed, it is cooled to room temperature after completion of the reaction, filters, and adds a small amount of water washing filter cake,
Filter cake drying, obtains methoxone 200.79g, content 98.5%, total recovery in terms of o-cresol 98.62%.
Embodiment 3
Into the phenol of 95.06g purity 99%, the sodium bicarbonate and 427.77g toluene of 91.65g purity 99% is added, rises
To moisture≤0.5%, the 2- chloropropionic acid N-butyl for being added dropwise to 179.62g purity 99% thereto at 80 DEG C makes warm reflux dewatering
Reaction, insulation reaction 0.5h at a temperature of this is added dropwise, is cooled to 50 DEG C, filtering, and suitable toluene washing filter is added
Cake dries to obtain sodium chloride and 2- phenoxy propionic acid N-butyl crude product containing toluene later, is distilled to recover toluene, while obtaining 2- benzene
Oxygroup n-butyl propionate 230.26g, content 96.0%.
Into distillation gained 2- phenoxy propionic acid N-butyl, the aluminium oxide and 0.12g purity of 1.73g purity 99% is added
99% tert-butylsulfide, the chlorine that 76.89g purity 99% is passed through at 100 DEG C are allowed to react, and addition finishes at a temperature of this
Insulation reaction 0.5h distills under 1kPa pressure and collects 130~140 DEG C of fraction, obtains the positive fourth of 2- (4- chlorophenoxy) propionic acid
Ester 257.60g, content 98.77%.
The phosphoric acid of 721.28g concentration 25% is added into gained 2- (4- chlorophenoxy) n-butyl propionate, it is sour at 80 DEG C
Solution reaction 3h, while the alcohol that reaction generates is steamed, end of reaction is cooled to room temperature, filters, and add a small amount of water washing filter cake, filter cake
Drying, obtains 2- (4- chlorophenoxy) propionic acid 199.92g, content 98.6%, total recovery in terms of phenol 98.29%.
Embodiment 4
Into the phenol of 95.06g purity 99%, the magnesium hydroxide and 285.18g benzene of 31.22g purity 99%, heating is added
To moisture≤0.5%, the positive last of the ten Heavenly stems ester of 2- chloropropionic acid for being added dropwise to 266.42g purity 99% thereto at 100 DEG C makes reflux dewatering
Reaction, insulation reaction 0.5h at a temperature of this is added dropwise, is cooled to 40 DEG C, filtering, and suitable benzene washing filter cake is added,
Magnesium chloride and the positive last of the ten Heavenly stems ester crude product of 2- phenoxy propionic acid containing benzene are dried to obtain later, are distilled to recover benzene, while obtaining 2- phenoxy group third
Sour positive last of the ten Heavenly stems ester 316.21g, content 96.1%.
Into the distillation gained positive last of the ten Heavenly stems ester of 2- phenoxy propionic acid, the magnesium chloride and 0.47g purity of 2.06g purity 99% is added
The 2 of 99%, 4,5- tri-tert isothiazole, the chlorine that 170.45g purity 99% is passed through at -20 DEG C are allowed to react, be added
Finish insulation reaction 0.5h at a temperature of this, 165~175 DEG C of fraction is distilled and collected under 1kPa pressure, obtains 2- (2,4- dichloros
Phenoxy group) the positive last of the ten Heavenly stems ester 374.49g of propionic acid, content 98.89%.
The trifluoromethanesulfonic acid of 1497.97g concentration 10% is added into the positive last of the ten Heavenly stems ester of gained 2- (2,4- dichlorophenoxy) propionic acid,
The acidolysis reaction 2h at 100 DEG C, while the alcohol that reaction generates is steamed, end of reaction is cooled to room temperature, filters, and add a small amount of washing
Filter cake is washed, filter cake drying obtains 2- (2,4- dichlorophenoxy) n-capric acid 233.55g, content 98.8%, total recovery is in terms of phenol
98.15%.
Embodiment 5
Into the phenol of 950.6g purity 99%, the sodium carbonate and 2376.5g dimethylbenzene of 556.7g purity 99% is added, rises
To moisture≤0.5%, the Isooctyl chloroacetate for being added dropwise to 2171.8g purity 99% thereto at 60 DEG C is allowed to warm reflux dewatering
Reaction, is added dropwise insulation reaction 0.5h at a temperature of this, is cooled to 40 DEG C, filters, and suitable dimethylbenzene washing filter is added
Cake dries to obtain sodium chloride and the different monooctyl ester crude product of phenoxy acetic acid containing dimethylbenzene later, is distilled to recover dimethylbenzene, while obtaining benzene oxygen
2-ethyl hexyl ethanoate 2728.6g, content 96.2%.
The chlorine that 45.5g load factor is 20% is separately added into thtee-stage shiplock flow reactor (each volume is 200ml)
Change 4,4 '-dichloro diphenyl sulfides/silica gel supported catalyst that zinc/silica gel supported catalyst and 9.1g load factor are 5%, to the
The 54.57g distillation gained different monooctyl ester of phenoxy acetic acid is added in first-stage reactor, then 27.34g is at the uniform velocity added at -20 DEG C in stirring
99% chlorosulfuric acid, to chlorosulfuric acid add followed by proportion at the uniform velocity be added 2674.0g distillation gained the different monooctyl ester of phenoxy acetic acid and
The chlorosulfuric acid of 1339.9g 99%, as material is from the addition of the first stage reactor, the continuous overflow of material enters the second order reaction
Device and third stage reactor, it is -20 DEG C that its temperature is kept when second, third stage reactor also has material, and reaction mass is last
System is gone out by third level reactor overflow, obtains the different monooctyl ester of 4-chlorophenoxyacetic acid, and loaded catalyst is since density is larger, no
It can be with material outflow system.Heat preservation 30min is finished to all materials addition, by the material filtering in the first, second and third stage reactor
Merge with the different monooctyl ester of 4-chlorophenoxyacetic acid gone out by third level reactor overflow, obtains the different monooctyl ester 2980.8g of 4-chlorophenoxyacetic acid, contain
Amount 99.12%.
The phosphoric acid of 8942.5g concentration 20%, the acidolysis reaction at 120 DEG C are added into the different monooctyl ester of gained 4-chlorophenoxyacetic acid
3h, while the alcohol that reaction generates is steamed, end of reaction is cooled to room temperature, it filters, and add a small amount of water washing filter cake, filter cake drying,
Obtain 4-chlorophenoxyacetic acid 1857.9g, content 98.9%, total recovery in terms of phenol 98.45%.
Embodiment 6
Into the o-cresol of 109.23g purity 99%, the potassium hydroxide solid and 546.16g of 64.20g content 90% is added
Dimethylbenzene, temperature rising reflux are dehydrated to moisture≤0.5%, are added dropwise to the 4- neoprene of 156.71g purity 99% thereto at 70 DEG C
Acetoacetic ester is allowed to react, and insulation reaction 0.5h at a temperature of this is added dropwise, and is cooled to 30 DEG C, filters, and be added suitable two
Toluene washs filter cake, dries to obtain potassium chloride and the adjacent toluene oxy butyrate ethyl ester containing dimethylbenzene later, is distilled to recover diformazan
Benzene, while obtaining adjacent toluene oxy butyrate ethyl ester 230.35g, content 96.0%.
Into the adjacent toluene oxy butyrate ethyl ester of distillation gained, the iron oxide and 1.96g purity 99% of 0.35g purity 99% is added
2,4,6- trimethylbenzene thioethers, the chlorine that 78.40g purity 99% is passed through at 0 DEG C is allowed to react, and addition is finished in this temperature
Lower insulation reaction 0.5h, distills under 1kPa pressure and collects 130~140 DEG C of fraction, obtains 4- chloro-2-methyl phenoxy butyric acid second
Ester 255.82g, content 99.29%.
The octadecyl sulfonic acid of 2046.53g concentration 5% is added into gained 4- chloro-2-methyl phenoxy butyric acid ethyl ester, in 85
Acidolysis reaction 2h at DEG C, while the alcohol that reaction generates is steamed, end of reaction is cooled to room temperature, filters, and add a small amount of water washing filter
Cake, filter cake drying, obtains 4- chloro-2-methyl phenoxy butyric acid 227.83g, content 98.7%, total recovery in terms of o-cresol 98.34%.
Embodiment 7
Into the o-cresol of 109.23g purity 99%, the saleratus and 218.46g first of 105.18g purity 99% is added
Benzene, temperature rising reflux are dehydrated to moisture≤0.5%, and the 4- chloro-butyric acid for being added dropwise to 246.66g purity 99% thereto at 90 DEG C is different
Monooctyl ester is allowed to react, and insulation reaction 0.5h at a temperature of this is added dropwise, and is cooled to 50 DEG C, filters, and suitable toluene is added
Filter cake is washed, dries to obtain potassium chloride and the different monooctyl ester crude product of adjacent toluene oxy butyrate containing toluene later, is distilled to recover toluene, simultaneously
Obtain the adjacent different monooctyl ester 318.89g of toluene oxy butyrate, content 95.8%.
Into the different monooctyl ester of the adjacent toluene oxy butyrate of distillation gained, the titanium dioxide and 0.80g purity of 1.75g purity 99% is added
99% 2- ethyl thiazole, the chlorine that 85.67g purity 99% is passed through at 50 DEG C are allowed to react, and addition finishes at a temperature of this
Insulation reaction 0.5h distills under 1kPa pressure and collects 160~170 DEG C of fraction, and it is different pungent to obtain 4- chloro-2-methyl phenoxy butyric acid
Ester 340.17g, content 99.08%.
The phosphoric acid of 680.33g concentration 35% is added into the different monooctyl ester of gained 4- chloro-2-methyl phenoxy butyric acid, it is sour at 95 DEG C
Solution reaction 3h, while the alcohol that reaction generates is steamed, end of reaction is cooled to room temperature, filters, and add a small amount of water washing filter cake, filter cake
Drying, obtains 4- chloro-2-methyl phenoxy butyric acid 227.67g, content 98.5%, total recovery in terms of o-cresol 98.03%.
Embodiment 8
Into the phenol of 95.06g purity 99%, 99% calcium hydroxide of 40.42g purity and 332.71g toluene, heating is added
For reflux dewatering to moisture≤0.5%, the methyl chloroacetate for being added dropwise to 118.40g purity 99% thereto at 80 DEG C is allowed to anti-
It answers, insulation reaction 0.5h at a temperature of this is added dropwise, be cooled to 30 DEG C, filter, and suitable toluene washing filter cake is added, it
Calcium chloride and methyl phenoxyacetate crude product containing toluene are dried to obtain afterwards, are distilled to recover toluene, while obtaining methyl phenoxyacetate
172.34g content 95.9%.
To distillation gained methyl phenoxyacetate in, be added 0.09g purity 99% lead acetate and 1.29g purity 99% 2,
3,4- tri- chlorothiophenes, the thionyl chloride that 118.34g purity 99% is added dropwise at 20 DEG C are allowed to react, and addition is finished in this temperature
Lower insulation reaction 0.5h, distills under 1kPa pressure and collects 110~120 DEG C of fraction, obtains 4-chlorophenoxyacetic acid methyl esters
200.87g content 98.84%.
The sulfuric acid of addition 401.74g concentration 25% into gained 4-chlorophenoxyacetic acid methyl esters, the acidolysis reaction 2h at 80 DEG C,
The alcohol that reaction generates is steamed simultaneously, and end of reaction is cooled to room temperature, filters, and add a small amount of water washing filter cake, and filter cake drying obtains 4-
Chlorophenoxyacetic acid 186.31g, content 98.6%, total recovery in terms of phenol 98.44%.
Embodiment 9
Into the phenol of 95.06g purity 99%, the potassium hydroxide solution and 190.12g of 116.88g concentration 48% is added
Benzene, temperature rising reflux are dehydrated to moisture≤0.5%, are added dropwise to the monoxone isopropyl of 137.97g purity 99% thereto at 110 DEG C
Ester is allowed to react, and insulation reaction 0.5h at a temperature of this is added dropwise, and is cooled to 40 DEG C, filters, and suitable benzene washing is added
Filter cake dries to obtain potassium chloride and the phenoxy acetic acid isopropyl ester crude product containing benzene later, is distilled to recover benzene, while it is different to obtain phenoxy acetic acid
Propyl ester 200.48g, content 96.1%.
Into distillation gained phenoxy acetic acid isopropyl ester, the titanium tetrachloride and 2.00g purity 99% of 0.70g purity 99% is added
3,4- dichloro-thiophene, the chlorosulfuric acid that 273.29g purity 99% is added dropwise at 70 DEG C is allowed to react, and addition is finished in this temperature
Lower insulation reaction 0.5h, distills under 1kPa pressure and collects 125~135 DEG C of fraction, obtains 2,4- dichlorphenoxyacetic acid isopropyl
Ester 261.91g, content 98.94%.
To gained 2, the hydrochloric acid of 2095.26g concentration 10%, the acidolysis at 60 DEG C are added in 4- dichlorphenoxyacetic acid isopropyl ester
4h is reacted, while steaming the alcohol that reaction generates, end of reaction is cooled to room temperature, filters, and add a small amount of water washing filter cake, filter cake dries
It is dry, obtain 2,4- dichlorphenoxyacetic acid 219.49g, content 98.8%, total recovery in terms of phenol 98.12%.
Embodiment 10
Into the o-cresol of 109.23g purity 99%, be added 127.50g concentration 32% sodium hydroxide solution and
436.93g toluene, temperature rising reflux are dehydrated to moisture≤0.5%, are added dropwise to 155.18g purity 99% thereto at 100 DEG C
Iso-butyl chloroacetate is allowed to react, and insulation reaction 0.5h at a temperature of this is added dropwise, and is cooled to 50 DEG C, filters, and is added suitable
The toluene of amount washs filter cake, dries to obtain sodium chloride and methylphenoxyacetic acid isobutyl ester crude product containing toluene later, is distilled to recover
Toluene, while obtaining methylphenoxyacetic acid isobutyl ester 229.29g, content 96.3%.
Into distillation gained methylphenoxyacetic acid isobutyl ester, the aluminium chloride and 1.03g purity of 0.57g purity 99% is added
The 4 of 99%, 4 '-thiobis (6- tert-butyl -3- methylphenol), are added dropwise to the chlorosulfuric acid of 139.49g purity 99% at 80 DEG C
It is allowed to react, addition finishes insulation reaction 0.5h at a temperature of this, distills under 1kPa pressure and collects 130~140 DEG C and evaporates
Point, obtain methoxone isobutyl ester 255.69g, content 99.09%.
The hydrochloric acid of 1150.59g concentration 20% is added into gained methoxone isobutyl ester, at 90 DEG C
Acidolysis reaction 4h, while the alcohol that reaction generates is steamed, end of reaction is cooled to room temperature, filters, and add a small amount of water washing filter cake, filter
Cake drying, obtains methoxone 198.67g, content 99.0%, total recovery in terms of o-cresol 98.03%.
Embodiment 11
Into the phenol of 950.6g purity 99%, the sodium bicarbonate and 4277.7g toluene of 916.5g purity 99% is added, rises
To moisture≤0.5%, the 2- chloropropionic acid N-butyl for being added dropwise to 1796.2g purity 99% thereto at 80 DEG C makes warm reflux dewatering
Reaction, insulation reaction 0.5h at a temperature of this is added dropwise, is cooled to 50 DEG C, filtering, and suitable toluene washing filter is added
Cake dries to obtain sodium chloride and 2- phenoxy propionic acid N-butyl crude product containing toluene later, is distilled to recover toluene, while obtaining 2- benzene
Oxygroup n-butyl propionate 2302.6g, content 96.0%.
Two that 26.9g load factor is 15% are separately added into thtee-stage shiplock flow reactor (each volume is 100ml)
2- methylthiophene/silica gel supported catalyst that titanium oxide/silica gel supported catalyst and 40.3g load factor are 10%, to the
30.0g distillation gained 2- phenoxy propionic acid N-butyl is added in first-stage reactor, then stirring is at the uniform velocity added at 100 DEG C
The chlorine of 10.0g 99% adds to chlorine and 2- phenoxy propionic acid N-butyl obtained by 2272.6g is followed by the uniform velocity added in proportion
With the chlorine of 758.9g 99%, as material is from the addition of the first stage reactor, the continuous overflow of material enters the second stage reactor
With third stage reactor, kept when second, third stage reactor also has material its temperature be 100 DEG C, reaction mass finally by
Third level reactor overflow goes out system, obtains 2- (4- chlorophenoxy) n-butyl propionate, and loaded catalyst due to density compared with
It greatly, will not be with material outflow system.Heat preservation 30min is finished to all materials addition, by the object in the first, second and third stage reactor
Material filtering merges with 2- (4- chlorophenoxy) n-butyl propionate gone out by third level reactor overflow, obtains 2- (4- chlorophenoxy) third
Sour N-butyl 2571.0g, content 98.96%.
The phosphoric acid of 7212.8g concentration 25% is added into gained 2- (4- chlorophenoxy) n-butyl propionate, it is sour at 80 DEG C
Solution reaction 3h, while the alcohol that reaction generates is steamed, end of reaction is cooled to room temperature, filters, and add a small amount of water washing filter cake, filter cake
Drying, obtains 2- (4- chlorophenoxy) propionic acid 1999.2g, content 98.5%, total recovery in terms of phenol 98.2%.
As seen from the above embodiment, phenoxy carboxylic acid herbicides product content >=98.5% obtained by the embodiment of the present invention, always
Yield >=98%, washing water and filtrate merge reuse.
Some target products and impurity situation are as follows in the embodiment of the present invention:
Some target products and impurity situation in 2 embodiment of the present invention of table
The present invention synthesizes benzene oxycarboxylic acid ester through condensation using phenol, and then selective chlorination synthesizes chlorobenzene oxycarboxylic acid ester, most
Acidolysis synthesizes phenoxy carboxylic acid herbicides afterwards.Present invention effectively avoids the production of the chlorinated phenol with bad smell and make
With, fundamentally prevented severe toxicity dioxin generation, greatly improve the operating environment of product quality and production scene.
Also, the present invention has effectively prevented the generation of high COD, high-salt wastewater, while the quantum of output of abraum salt (metal chloride) reduces
50% or more, significantly reduce three-protection design amount, three-protection design difficulty and processing cost.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of phenoxy carboxylic acid herbicides, comprising the following steps:
S1, by phenol or o-cresol in the presence of alkaline substances, carry out condensation reaction with chlorinated carboxylic acid ester, obtain benzene oxygen
Carboxylate；
The general formula of the chlorinated carboxylic acid ester is ClR1COOR, wherein R1The alkylidene or alkylidene for being 1~3 selected from carbon atom number, R
Selected from carbon atom number be 1~10 alkyl or carbon atom number be 3~10 naphthenic base；
S2, by the benzene oxycarboxylic acid ester existing for the first catalyst and the second catalyst under the conditions of, selected with chlorinating agent
Property chlorination, obtains chlorobenzene oxycarboxylic acid ester；First catalyst is selected from lewis acid, and second catalyst is selected from carbon atom
Count the isothiazole that the thio-ether type compounds for 5~22, the thiazole compound that carbon atom number is 5~22, carbon atom number are 5~22
The thiophenes that class compound or carbon atom number are 5~22；
S3, the chlorobenzene oxycarboxylic acid ester is subjected to acidolysis reaction, obtains phenoxy carboxylic acid herbicides shown in Formulas I；
In Formulas I, R1The alkylidene or alkylidene for being 1~3 selected from carbon atom number, R3For H, Cl or CH3。
2. preparation method according to claim 1, which is characterized in that in S1 step, the alkaline matter be sodium hydroxide,
Potassium hydroxide, calcium hydroxide, magnesium hydroxide, sodium bicarbonate, saleratus, sodium carbonate or potassium carbonate.
3. preparation method according to claim 2, which is characterized in that in S1 step, the alkaline matter be sodium hydroxide,
The molar ratio of potassium hydroxide, sodium bicarbonate or saleratus, the phenol or o-cresol and alkaline matter is 1:(1~1.08)；
Alternatively, the alkaline matter is calcium hydroxide, magnesium hydroxide, sodium carbonate or potassium carbonate, the phenol or o-cresol and alkali
Property substance molar ratio be 1:(0.5~0.54).
4. preparation method according to claim 1, which is characterized in that in S1 step, the condensation reaction is in organic solvent
Middle progress, the organic solvent are benzene, toluene or dimethylbenzene.
5. the preparation method according to claim 4, which is characterized in that in S1 step, the dosage of the organic solvent is benzene
1~5 times of phenol or o-cresol weight.
6. preparation method according to claim 1, which is characterized in that in S1 step, the phenol or o-cresol and chloro
The molar ratio of carboxylate is 1:(1~1.08), the temperature of the condensation reaction is 60~120 DEG C.
7. preparation method according to claim 1, which is characterized in that in S2 step, the chlorinating agent is chlorine, thionyl
Chlorine or chlorosulfuric acid.
8. preparation method according to claim 7, which is characterized in that in S2 step, the benzene oxycarboxylic acid ester and chlorinating agent
Molar ratio be 1:(1.98~2.4), R in S3 step3For Cl；
Alternatively, the molar ratio of the benzene oxycarboxylic acid ester and chlorinating agent is 1:(0.99~1.2), R in S3 step3For H or CH3。
9. preparation method according to claim 1, which is characterized in that in S2 step, the dosage of first catalyst is
The 0.05%~1.0% of benzene oxycarboxylic acid ester weight, the dosage of second catalyst be benzene oxycarboxylic acid ester weight 0.05%~
1.0%.
10. the preparation method according to any one of claim 7~9, which is characterized in that in S2 step, the selectivity
The temperature of chlorination reaction is -20~100 DEG C.
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| PCT/CN2019/075306 WO2019179265A1 (en) | 2018-03-19 | 2019-02-18 | Method for preparing phenoxy carboxylic acid herbicide |
| ARP190100680A AR115273A1 (en) | 2018-03-19 | 2019-03-19 | METHOD FOR THE PREPARATION OF PHENOXICARBOXYLIC ACID HERBICIDE |
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| WO2019179267A1 (en) * | 2018-03-19 | 2019-09-26 | 山东润博生物科技有限公司 | Preparation method of phenoxycarboxylic acid herbicides |
| WO2019179265A1 (en) * | 2018-03-19 | 2019-09-26 | 山东润博生物科技有限公司 | Method for preparing phenoxy carboxylic acid herbicide |
| CN113173844A (en) * | 2021-05-11 | 2021-07-27 | 宁夏格瑞精细化工有限公司 | Preparation method of 2-methyl-4-chlorophenoxyacetic acid |
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| CN114904575A (en) * | 2022-06-28 | 2022-08-16 | 万华化学集团股份有限公司 | Catalyst and preparation method thereof, and preparation method of 3, 6-dialkoxy-2, 7-dimethyl-4-octenedialdehyde |
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| 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 |
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| US3920757A (en) * | 1971-08-25 | 1975-11-18 | Dow Chemical Co | Chlorination with sulfuryl chloride |
| CN106278862B (en) * | 2016-08-04 | 2019-06-25 | 山东省化工研究院 | A kind of new technique for synthesizing of 2,4 dichlorophenoxyacetic acid |
| CN108947838A (en) * | 2018-03-19 | 2018-12-07 | 山东润博生物科技有限公司 | A kind of preparation method of 2,4 dichlorophenoxyacetic acid and its salt |
| CN108947794A (en) * | 2018-03-19 | 2018-12-07 | 山东润博生物科技有限公司 | A kind of preparation method of phenoxy carboxylic acid herbicides |
| CN108947822A (en) * | 2018-03-19 | 2018-12-07 | 山东润博生物科技有限公司 | A kind of preparation method of phenoxy carboxylic acid herbicides |
| CN108947792A (en) * | 2018-03-19 | 2018-12-07 | 山东润博生物科技有限公司 | A kind of preparation method of phenoxy carboxylic acid herbicides |
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| 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 |
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|---|---|---|---|---|
| WO2019179267A1 (en) * | 2018-03-19 | 2019-09-26 | 山东润博生物科技有限公司 | Preparation method of phenoxycarboxylic acid herbicides |
| WO2019179265A1 (en) * | 2018-03-19 | 2019-09-26 | 山东润博生物科技有限公司 | Method for preparing phenoxy carboxylic acid herbicide |
| US11040933B2 (en) | 2018-03-19 | 2021-06-22 | Shandong Rainbow Biotech Co., Ltd. | Preparation method of phenoxycarboxylic acid herbicides |
| CN113173844A (en) * | 2021-05-11 | 2021-07-27 | 宁夏格瑞精细化工有限公司 | Preparation method of 2-methyl-4-chlorophenoxyacetic acid |
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| WO2019179265A1 (en) | 2019-09-26 |
| AR115273A1 (en) | 2020-12-16 |
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