CN108947804A - A kind of preparation method of chlorobenzene oxycarboxylic acid substance - Google Patents
A kind of preparation method of chlorobenzene oxycarboxylic acid substance Download PDFInfo
- Publication number
- CN108947804A CN108947804A CN201810226106.1A CN201810226106A CN108947804A CN 108947804 A CN108947804 A CN 108947804A CN 201810226106 A CN201810226106 A CN 201810226106A CN 108947804 A CN108947804 A CN 108947804A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- preparation
- thiazole
- variety
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/285—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with peroxy-compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/363—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of preparation methods of chlorobenzene oxycarboxylic acid substance, comprising: S1) by benzene oxygen fatty alcohol, oxidant, oxidation catalyst and alkaline matter hybrid reaction shown in formula (I), after filtering, obtain reaction solution；S2) by the reaction solution, catalyst A, catalyst B and chlorinating agent hybrid reaction, chlorobenzene oxycarboxylic acid substance shown in formula (II) is obtained.Compared with prior art, the present invention is by the way that by benzene oxygen fatty alcohol, first direct oxidation obtains benzene oxygen fatty acid salt in oxidation catalyst and alkaline environment, chlorobenzene oxycarboxylic acid substance is obtained in catalytic chlorination again, without cumbersome concentration unit, process is simple, is not necessarily to high temperature, low energy consumption, selectivity is high, and consumption of raw materials is low, and waste water abraum salt amount is low.
Description
Technical field
The invention belongs to technical field of organic synthesis more particularly to a kind of preparation methods of chlorobenzene oxycarboxylic acid substance.
Background technique
Currently, phenoxy carboxylic acid substance is widely used in herbicide pesticide.Nineteen forty-one has synthesized first phenoxy carboxylic acid and has removed
The kind 2 of careless agent, 4- dichlorphenoxyacetic acid, nineteen forty-two have found that the compound has the function of plant hormone, nineteen forty-four discovery
2,4- dichlorphenoxyacetic acids and 2,4,5- tears have activity of weeding, 2 first of discovery herbicide, 4 chlorine in 1945 to field bindweed.It is such to remove
Selectivity, conductibility and the removing activity that careless agent is shown become the basis of herbicide development thereafter, promote the hair of chemical weed control
Exhibition.
Difference of the phenoxy carboxylic acid herbicides according to its active constituent body compound can be divided into two different fundamental systems
Column.One is being ontology with 2,4- Dichlorophenol, such as 2,4- dichlorphenoxyacetic acid (2,4- drops acid), 2,4- Dichlorophenoxy propionic acid
(2,4- drop P), 2,4 dichloro benzene oxy butyrate (2,4- drop B)；Another kind is such as 2 first, 4 chloric acid using o-cresol as ontology
(MCPA), Vi par (MCPP), Thistrol (MCPB).
The synthetic method of 2,4- Dichlorophenoxy carboxylic acid disclosed in the prior art mainly uses Williamson condensation method, production
Technique is: chlorophenesic acid, at salt, then carries out in water phase with chlorinated carboxylic acid, alkali neutralization at salt product again in water phase
Williamson condensation reaction obtains benzene oxycarboxylic acid salt, is then acidified again, obtains raw medicine after obtaining benzene oxycarboxylic acid filtering drying.
But such method has the disadvantage in that, 1) from raw material, which obtains 2,4- dichloro-benzenes using phenol chlorination
Phenol, 2,4- chlorophenesic acid smells are very big, and hypertoxic carcinogen dioxin is generated when condensation；2) from process flow, the technique
Process is complicated, and first chlorination obtains chlorophenol, then synthesizes phenol sodium, and monoxone configuration neutralizes material, is then condensed, is acidified, process is complicated；
3) environmentally friendly disadvantage, the technique are carried out in water phase using phenol sodium and chlorinated carboxylic acid sodium, chlorinated carboxylic acid sodium pole under alkali cleaning water environment
It is high to lead to chlorinated carboxylic acid sodium waste, and then leads to high organic content in waste water for facile hydrolysis, and wastewater flow rate is big.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that providing a kind of system of chlorobenzene oxycarboxylic acid ester type compound
Preparation Method, the preparation method is simple and yield is higher.
The present invention provides a kind of preparation methods of chlorobenzene oxycarboxylic acid substance, comprising:
S1) by benzene oxygen fatty alcohol, oxidant, oxidation catalyst and alkaline matter hybrid reaction shown in formula (I), filtering
Afterwards, reaction solution is obtained；
S2) by the reaction solution, catalyst A, catalyst B and chlorinating agent hybrid reaction, chloro shown in formula (II) is obtained
Phenoxy carboxylic acid substance；The catalyst A is lewis acid；The catalyst B is thioether, thiazole, the substituted thiophene of C5~C22
One of azoles, isothiazole, substituted isothiazole, thiophene and substituted thiophene are a variety of；It is the substituted thiazole, substituted different
Substituent group in thiazole and substituted thiophene is each independently selected from one of the alkyl of C1~C5 and halogen or a variety of；
Wherein, R is the alkyl of H or C1~C4；R1For the alkyl of H or C1~C5；
R2For Cl or H, and R1For C1~C5 alkyl when R2It is not Cl.
Preferably, the oxidation catalyst is selected from one of cobalt compound, manganese salt, vanadic salts, zirconates and tungsten salt or more
Kind.
Preferably, the oxidation catalyst be selected from cobalt acetate, cobalt naphthenate, four water manganese acetates, manganese chloride, sodium metavanadate,
One of zirconium chloride and eight carbonyl cobalts are a variety of.
Preferably, the quality of the oxidation catalyst is 1%~10% of benzene oxygen fatty alcohol quality shown in formula (I).
Preferably, the oxidant is selected from one of hydrogen peroxide, oxygen and ozone or a variety of；The alkaline matter is selected from
One of sodium hydroxide, potassium hydroxide, calcium hydroxide and magnesium hydroxide are a variety of.
Preferably, the catalyst A is selected from SnCl4、MgCl2、FeCl3、AlCl3、BF3、ZnCl2、TiCl4、SbF5、
Al2O3、Fe2O3、TiO2、Pb(OAc)2、Zn(OAc)2With Al2O(OAc)4One of or it is a variety of.
Preferably, the catalyst B is selected from tertbutyl methyl thioether, tert-butylsulfide, diphenyl sulfide, 4,4 '-dichloro-benzenes sulphur
Ether, 2- methyl diphenyl sulfide, 2,4,6- trimethylbenzene thioether, 4,4 '-thiobis (6- tert-butyl -3- methylphenol), thiazole, 2- second
Base thiazole, 2,5- dichloro thiazole, 4- methylthiazol, 2- tertiary butyl thiazole, isothiazole, 4,5- dimethyl isothiazole, the different thiophene of 5- chlorine
Azoles, 2,4,5- tri-tert isothiazole, thiophene, 2- methylthiophene, 2,5- thioxene, 3- chlorothiophene, 3,4- dichloro-thiophene
With one of tri- chlorothiophene of 2,3,4- or a variety of.
Preferably, the quality of the catalyst A is 0.05%~1.0% of benzene oxygen fatty alcohol quality shown in formula (I).
Preferably, the quality of the catalyst B is 0.05%~1.0% of benzene oxygen fatty alcohol quality shown in formula (I).
Preferably, the step S2) in after hybrid reaction, adding acid for adjusting pH value is 1~2, is cooled down, and filtering obtains
Chloro phenoxy carboxylic acid compound shown in formula (II).
The present invention provides a kind of preparation methods of chlorobenzene oxycarboxylic acid substance, comprising: S1) by benzene shown in formula (I)
Oxygen fatty alcohol, oxidant, oxidation catalyst and alkaline matter hybrid reaction, after filtering, obtain reaction solution；S2) by the reaction
Liquid, catalyst A, catalyst B and chlorinating agent hybrid reaction obtain chlorobenzene oxycarboxylic acid substance shown in formula (II)；It is described to urge
Agent A is lewis acid；The catalyst B is thioether, thiazole, substituted thiazole, isothiazole, the substituted different thiophene of C5~C22
One of azoles, thiophene and substituted thiophene are a variety of；In the substituted thiazole, substituted isothiazole and substituted thiophene
Substituent group is each independently selected from one of the alkyl of C1~C5 and halogen or a variety of；Wherein, R is the alkyl of H or C1~C4；
R1For the alkyl of H or C1~C5；R2For Cl or H, and R1For C1~C5 alkyl when R2It is not Cl.Compared with prior art, this hair
It is bright by the way that by benzene oxygen fatty alcohol, first direct oxidation obtains benzene oxygen fatty acid salt in oxidation catalyst and alkaline environment, then be catalyzed
Chlorination obtains chlorobenzene oxycarboxylic acid substance, and without cumbersome concentration unit, process is simple, is not necessarily to high temperature, and low energy consumption, selectivity
Height, consumption of raw materials is low, and waste water abraum salt amount is low.
Detailed description of the invention
Fig. 1 is to obtain the liquid chromatogram of 2,4 dichloro benzene oxycarboxylic acid in the embodiment of the present invention 1.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme in the embodiment of the invention is clearly and completely described,
Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based in the present invention
Embodiment, every other embodiment obtained by those of ordinary skill in the art without making creative efforts, all
Belong to the scope of protection of the invention.
The present invention provides a kind of preparation methods of chlorobenzene oxycarboxylic acid substance, comprising: S1) by benzene shown in formula (I)
Oxygen fatty alcohol, oxidant, oxidation catalyst and alkaline matter hybrid reaction, after filtering, obtain reaction solution；S2) by the reaction
Liquid, catalyst A, catalyst B and chlorinating agent hybrid reaction obtain chlorobenzene oxycarboxylic acid substance shown in formula (II)；It is described to urge
Agent A is lewis acid；The catalyst B is thioether, thiazole, substituted thiazole, isothiazole, the substituted different thiophene of C5~C22
One of azoles, thiophene and substituted thiophene are a variety of；In the substituted thiazole, substituted isothiazole and substituted thiophene
Substituent group is each independently selected from one of the alkyl of C1~C5 and halogen or a variety of；
Wherein, R is the alkyl of H or C1~C4, the alkane of the alkyl of preferably H or C1~C3, more preferably H or C1~C2
Base；R1For the alkyl of H or C1~C5, the alkyl of the alkyl of preferably H or C1~C4, more preferably H or C1~C3, further preferably for
The alkyl of H or C1~C2；R2For Cl or H, and R1For C1~C5 alkyl when R2It is not Cl.
The present invention is not particularly limited the source of all raw materials, is commercially available.
By benzene oxygen fatty alcohol, oxidant, oxidation catalyst and alkaline matter hybrid reaction shown in formula (I)；The oxidation
Agent is oxidant well known to those skilled in the art, has no special limitation, in the present invention preferably hydrogen peroxide, oxygen with
One of ozone is a variety of, more preferably oxygen；The molar ratio of benzene oxygen fatty alcohol shown in the formula (I) and oxidant is preferred
For 1:(1~2), more preferably 1:(1.05~1.5), it is further preferably 1:(1.05~1.2)；The oxidation catalyst is this field
Oxidation catalyst known to technical staff has no special limitation, is preferably cobalt compound, manganese salt, vanadium in the present invention
One of salt, zirconates and tungsten salt are a variety of, more preferably cobalt acetate, cobalt naphthenate, four water manganese acetates, manganese chloride, metavanadic acid
One of sodium, zirconium chloride and eight carbonyl cobalts are a variety of；The quality of the oxidation catalyst is preferably benzene oxygen rouge shown in formula (I)
The 1%~10% of fat alcohol quality, more preferably 2%~8%, it is further preferably 2%~5%；The alkaline matter is this field skill
Alkaline matter known to art personnel has no special limitation, is preferably sodium hydroxide, potassium hydroxide, hydrogen-oxygen in the present invention
Change one of calcium and magnesium hydroxide or a variety of；The molar ratio of the alkaline matter and benzene oxygen fatty alcohol shown in formula (I) is preferred
For 1:(1~1.5), more preferably 1:(1.1~1.2)；The reaction preferably carries out in water；The quality of the water is preferably formula
(I) 1.5~4 times of benzene oxygen fatty alcohol quality, more preferably 1.5~3 times shown in are further preferably 2~2.5 times；The mixing
The temperature of reaction is preferably 30 DEG C~60 DEG C；The time of the hybrid reaction is preferably 2~for 24 hours, more preferably 8~15h；At this
In invention, after preferably first mixing benzene oxygen fatty alcohol, oxidation catalyst shown in formula (I) with alkaline matter, it is heated to reaction temperature
Degree, adds oxidant reaction.
After reaction, filtering separates and recovers oxidation catalyst, obtains reaction solution.
By the reaction solution, catalyst A, catalyst B and chlorinating agent hybrid reaction；The catalyst A is lewis acid,
For lewis acid well known to those skilled in the art, special limitation is had no, is preferably pink salt, magnesium salts, iron in the present invention
Salt, aluminium salt, aluminium salt, zinc salt, titanium salt, antimonic salt and BF3One of or a variety of, more preferably SnCl4、MgCl2、FeCl3、AlCl3、
BF3、ZnCl2、TiCl4、SbF5、Al2O3、Fe2O3、TiO2、Pb(OAc)2、Zn(OAc)2With Al2O(OAc)4One of or it is more
Kind；The quality of the catalyst A is preferably 0.05%~1.0% of benzene oxygen fatty alcohol quality shown in formula (I), more preferably
0.25%~1.0%, it is further preferably 0.5%~1.0%；The catalyst B is thioether, thiazole, the substituted thiophene of C5~C22
One of azoles, isothiazole, substituted isothiazole, thiophene and substituted thiophene are a variety of；It is the substituted thiazole, substituted different
Substituent group in thiazole and substituted thiophene is each independently selected from one of the alkyl of C1~C5 and halogen or a variety of, more excellent
It is selected as tertbutyl methyl thioether, tert-butylsulfide, diphenyl sulfide, 4,4 '-dichloro diphenyl sulfides, 2- methyl diphenyl sulfide, 2,4,6- front three
Base diphenyl sulfide, 4,4 '-thiobis (6- tert-butyl -3- methylphenol), thiazole, 2- ethyl thiazole, 2,5- dichloro thiazole, 4- methyl
Thiazole, 2- tertiary butyl thiazole, isothiazole, 4,5- dimethyl isothiazole, 5- chloroisothiazole, 2,4,5- tri-tert isothiazole, thiophene
One of pheno, 2- methylthiophene, 2,5- thioxene, tri- chlorothiophene of 3- chlorothiophene, 3,4- dichloro-thiophene and 2,3,4- or
It is a variety of, be further preferably tert-butylsulfide, 2,4,6- trimethylbenzene thioethers, 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 with
One of 2,3,4- tri- chlorothiophenes are a variety of, most preferably tert-butylsulfide, 4,4 '-thiobis (6- tert-butyl -3- methylbenzene
Phenol), one of tri- chlorothiophene of 2,4,5- tri-tert isothiazole and 2,3,4- or a variety of；The quality of the catalyst B is preferred
It is 0.05%~1.0%, more preferably 0.2%~0.8% of benzene oxygen fatty alcohol quality shown in formula (I), further preferably for 0.3%~
0.5%；The chlorinating agent is chlorinating agent well known to those skilled in the art, has no special limitation, in the present invention preferably
For one of chlorine, thionyl chloride, chlorosulfuric acid, phosgene (phosgene) and two (trichloromethyl) carbonic esters (solid phosgene) or more
Kind, more preferably one of chlorine, thionyl chloride and chlorosulfuric acid or a variety of, are further preferably chlorine and/or chlorosulfuric acid；The chlorine
The molar ratio of fatty alcohol shown in agent and formula (I) is optionally depending on the number of chloro, when needing the number of chloro to be 1, institute
The molar ratio for stating benzene oxygen fatty alcohol shown in formula (I) and chlorinating agent is preferably 1:(0.98~1.2), more preferably 1:(1~
It 1.1) is further preferably, 1:(1.01~1.03)；When substituted number is 2, benzene oxygen fatty alcohol and chlorine shown in the formula (I)
The molar ratio of agent is preferably 1:(1.98~2.4), more preferably 1:(2~2.2), it is further preferably 1:(2.02~2.06)；Institute
The temperature for stating hybrid reaction is preferably -20 DEG C~100 DEG C, and more preferably -20 DEG C~60 DEG C, be further preferably -20 DEG C~40 DEG C, most
Preferably -20 DEG C~20 DEG C；The time of the hybrid reaction is preferably 0.5~2h, more preferably 0.5~1h；In the mixing
The pH value that reaction solution is preferably remained during reaction is 9~11, more preferably 9.5~10.5, is further preferably 10.
After hybrid reaction, preferably plus acid for adjusting pH value is 1~2, is cooled down, filtering obtains chlorobenzene oxygen shown in formula (II)
Carboxylic acid compound.
The reaction equation of the preparation method of chloro phenoxy carboxylic acid compound provided by the invention is as follows:
The present invention is by the way that by benzene oxygen fatty alcohol, first direct oxidation obtains benzene oxygen fat in oxidation catalyst and alkaline environment
Hydrochlorate, then chlorobenzene oxycarboxylic acid substance is obtained in catalytic chlorination, without cumbersome concentration unit, process is simple, it is not necessarily to high temperature,
Low energy consumption, and selectivity is high, and consumption of raw materials is low, and waste water abraum salt amount is low.
In order to further illustrate the present invention, with reference to embodiments to a kind of chloro phenoxy carboxylic acid object provided by the invention
The preparation method of matter is described in detail.
Reagent used in following embodiment is commercially available.
Embodiment 1
Phenoxyethanol 139.6g (1mol), water 300g, 40.5g (1mol) sodium hydroxide are mixed with 3.1g cobalt acetate, added
The hydrogen peroxide for entering 350g 10% is warming up to 80 DEG C or so and is kept for 12 hours, and inspection does not turn, after not turning qualification, is reduced to room
Temperature filtering removal molecular sieve catalyst, filtrate are directly added into 0.28g iron chloride and 0.3g dimethyl sulphide, are passed through chlorine, in the process
It keeps pH 10 or so, after to be chlorinated, sees salt acid for adjusting pH to 1 or so, product 214.1g, purity are dried to obtain in filtering
98.2%, yield 95.1%.
Obtained product is analyzed using high performance liquid chromatography, obtains liquid chromatogram as shown in Figure 1, obtaining liquid phase
Chromatographic results are shown in Table 1.
1 liquid chromatography results of table
| Peak number | Retention time | Area | Highly | Area % |
| 1 | 2.228 | 9268 | 389 | 0.065 |
| 2 | 2.809 | 35812 | 3969 | 0.253 |
| 3 | 4.083 | 1660 | 184 | 0.012 |
| 4 | 4.702 | 11828 | 876 | 0.083 |
| 5 | 6.186 | 7996 | 565 | 0.056 |
| 6 | 9.435 | 14105413 | 788834 | 99.53 |
| It amounts to | 14171977 | 794818 | 100 |
Embodiment 2
Phenoxyethanol 139.6g (1mol), water 300g, 40.5g (1mol) sodium hydroxide are mixed with 1.6g manganese chloride, added
The hydrogen peroxide for entering 350g 10% is warming up to 160 DEG C or so and is kept for 12 hours, and inspection does not turn, after not turning qualification, is reduced to
Room temperature filtering removal chlorination Mn catalyst, filtrate are directly added into 0.28g magnesium chloride and 0.31g dimethyl benzene thioether, are passed through chlorine,
It keeping pH 10 or so in the process, after to be chlorinated, sees salt acid for adjusting pH to 1 or so, product 216.1g is dried to obtain in filtering,
Purity 98.2%, yield 96.2%.
Embodiment 3
Adjacent toluene oxyethanol 153.6g (1mol), water 300g, 40.5g (1mol) sodium hydroxide and 3.1g cobalt acetate is mixed
It closes, the hydrogen peroxide of 350g 10% is added, be warming up to 80 DEG C or so and kept for 12 hours, inspection does not turn, after not turning qualification, drop
Removal molecular sieve catalyst is filtered as low as room temperature, filtrate is directly added into 0.28g iron chloride and 0.3g dimethyl sulphide, is passed through chlorine,
It keeping pH 10 or so in the process, after to be chlorinated, sees salt acid for adjusting pH to 1 or so, product 193.8g is dried to obtain in filtering,
Purity 98.6%, yield 95.1%.
Embodiment 4
Adjacent toluene oxyethanol 153.6g (1mol), water 300g, 40.5g (1mol) sodium hydroxide and 1.6g manganese chloride is mixed
It closes, the hydrogen peroxide of 350g 10% is added, be warming up to 160 DEG C or so and kept for 12 hours, inspection does not turn, after not turning qualification, drop
Removal chlorination Mn catalyst is filtered as low as room temperature, filtrate is directly added into 0.28g magnesium chloride and 0.31g dimethyl benzene thioether, is passed through
Chlorine keeps pH 10 or so in the process, after to be chlorinated, sees salt acid for adjusting pH to 1 or so, product is dried to obtain in filtering
194.1g, purity 98.2%, yield 96.2%.
Claims (10)
1. a kind of preparation method of chlorobenzene oxycarboxylic acid substance characterized by comprising
S1 it) by benzene oxygen fatty alcohol, oxidant, oxidation catalyst and alkaline matter hybrid reaction shown in formula (I), after filtering, obtains
To reaction solution；
S2) by the reaction solution, catalyst A, catalyst B and chlorinating agent hybrid reaction, chlorobenzene oxygen shown in formula (II) is obtained
Carboxylic-acid substance；The catalyst A is lewis acid；The catalyst B be the thioether of C5~C22, thiazole, substituted thiazole,
One of isothiazole, substituted isothiazole, thiophene and substituted thiophene are a variety of；The substituted thiazole, substituted different thiophene
Substituent group in azoles and substituted thiophene is each independently selected from one of the alkyl of C1~C5 and halogen or a variety of；
Wherein, R is the alkyl of H or C1~C4；R1For the alkyl of H or C1~C5；
R2For Cl or H, and R1For C1~C5 alkyl when R2It is not Cl.
2. preparation method according to claim 1, which is characterized in that the oxidation catalyst is selected from cobalt compound, manganese
One of salt, vanadic salts, zirconates and tungsten salt are a variety of.
3. preparation method according to claim 1, which is characterized in that the oxidation catalyst is selected from cobalt acetate, aphthenic acids
One of cobalt, four water manganese acetates, manganese chloride, sodium metavanadate, zirconium chloride and eight carbonyl cobalts are a variety of.
4. preparation method according to claim 1, which is characterized in that the quality of the oxidation catalyst is shown in formula (I)
Benzene oxygen fatty alcohol quality 1%~10%.
5. preparation method according to claim 1, which is characterized in that the oxidant is selected from hydrogen peroxide, oxygen and ozone
One of or it is a variety of；The alkaline matter be selected from one of sodium hydroxide, potassium hydroxide, calcium hydroxide and magnesium hydroxide or
It is a variety of.
6. preparation method according to claim 1, which is characterized in that the catalyst A is selected from SnCl4、MgCl2、FeCl3、
AlCl3、BF3、ZnCl2、TiCl4、SbF5、Al2O3、Fe2O3、TiO2、Pb(OAc)2、Zn(OAc)2With Al2O(OAc)4One of
Or it is a variety of.
7. preparation method according to claim 1, which is characterized in that the catalyst B is selected from tertbutyl methyl thioether, uncle
Butyl thioether, diphenyl sulfide, 4,4 '-dichloro diphenyl sulfides, 2- methyl diphenyl sulfide, 2,4,6- trimethylbenzene thioether, 4,4 '-thiobis
It is (6- tert-butyl -3- methylphenol), thiazole, 2- ethyl thiazole, 2,5- dichloro thiazole, 4- methylthiazol, 2- tertiary butyl thiazole, different
Thiazole, 4,5- dimethyl isothiazole, 5- chloroisothiazole, 2,4,5- tri-tert isothiazole, thiophene, 2- methylthiophene, 2,5- bis-
One of methylthiophene, tri- chlorothiophene of 3- chlorothiophene, 3,4- dichloro-thiophene and 2,3,4- are a variety of.
8. preparation method according to claim 1, which is characterized in that the quality of the catalyst A is benzene shown in formula (I)
The 0.05%~1.0% of oxygen fatty alcohol quality.
9. preparation method according to claim 1, which is characterized in that the quality of the catalyst B is benzene shown in formula (I)
The 0.05%~1.0% of oxygen fatty alcohol quality.
10. preparation method according to claim 1, which is characterized in that the step S2) in after hybrid reaction, add
Acid for adjusting pH value is 1~2, is cooled down, and filtering obtains chloro phenoxy carboxylic acid compound shown in formula (II).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810226106.1A CN108947804A (en) | 2018-03-19 | 2018-03-19 | A kind of preparation method of chlorobenzene oxycarboxylic acid substance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810226106.1A CN108947804A (en) | 2018-03-19 | 2018-03-19 | A kind of preparation method of chlorobenzene oxycarboxylic acid substance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108947804A true CN108947804A (en) | 2018-12-07 |
Family
ID=64495225
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810226106.1A Withdrawn CN108947804A (en) | 2018-03-19 | 2018-03-19 | A kind of preparation method of chlorobenzene oxycarboxylic acid substance |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108947804A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109096176A (en) * | 2018-10-03 | 2018-12-28 | 淮安安莱生物科技有限公司 | A kind of preparation method of Ondansetron impurity D |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102336654A (en) * | 2011-07-14 | 2012-02-01 | 大连化工研究设计院 | Chloration method for phenoxyacetic acid and derivatives thereof |
-
2018
- 2018-03-19 CN CN201810226106.1A patent/CN108947804A/en not_active Withdrawn
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102336654A (en) * | 2011-07-14 | 2012-02-01 | 大连化工研究设计院 | Chloration method for phenoxyacetic acid and derivatives thereof |
Non-Patent Citations (1)
| Title |
|---|
| 张聪等: "氧气催化氧化法苯氧乙醇合成苯氧乙酸", 《精细化工》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109096176A (en) * | 2018-10-03 | 2018-12-28 | 淮安安莱生物科技有限公司 | A kind of preparation method of Ondansetron impurity D |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108947794A (en) | A kind of preparation method of phenoxy carboxylic acid herbicides | |
| CN104387303B (en) | The asymmetric over cure compound of aryl-aryl, aryl-alkyl, alkyl-alkyl and synthetic method thereof | |
| CN108947822A (en) | A kind of preparation method of phenoxy carboxylic acid herbicides | |
| US7759527B2 (en) | Microwave induced one pot process for the preparation of arylethenes | |
| CN105294419A (en) | Synthesis methods of 3, 6-dichloro-2-methoxybenzoic acid and its intermediate | |
| CN112707799B (en) | Method for preparing 3,4' -dichlorodiphenyl ether from difenoconazole isomer | |
| CN108947804A (en) | A kind of preparation method of chlorobenzene oxycarboxylic acid substance | |
| CN106916060A (en) | A kind of preparation method of high-purity parahydroxyacet-ophenone | |
| CN106892808A (en) | A kind of preparation method of 2,4 dichlorphenoxyacetic acids | |
| WO2019179287A2 (en) | Preparation method for 2,4-dichlorophenoxyacetic acid or salt thereof | |
| CN101260092B (en) | Method for preparing cinepazide maleate | |
| CN102716768B (en) | 2-aryl-zinc-propionate catalyst and preparation method and application thereof | |
| CN108947803A (en) | A kind of preparation method of phenoxy carboxylic acid substance | |
| CN108947814A (en) | A kind of preparation method of benzene oxycarboxylic acid ester herbicide | |
| CN109776301A (en) | The synthetic method of one kind 2,4- dichlorphenoxyacetic acid compound | |
| WO2019179288A2 (en) | Preparation method for chlorophenoxycarboxylate | |
| CN108503525A (en) | The preparation method of one kind 2,4- dichlorphenoxyacetic acids | |
| WO2020001047A2 (en) | Preparation method for phenoxycarboxylic acid herbicide | |
| CN108947837A (en) | A kind of preparation method of 2,4 dichlorophenoxyacetic acid ester | |
| CN109467509A (en) | A kind of preparation method of substituted mirbane oil compound | |
| CN111377831A (en) | Preparation method of herbicide cyhalofop-butyl | |
| CN108947811A (en) | A kind of preparation method of benzene oxycarboxylic acid salt herbicide | |
| CN108947821A (en) | A kind of preparation method of chlorobenzene oxycarboxylic acid ester | |
| CN109761788A (en) | The preparation method of the bromo- 3,6- dichlorobenzoic acid of 2- and the preparation method of dicamba | |
| US11078150B2 (en) | Preparation method for chlorophenoxycarboxylate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20181207 |