CN108947799A - A kind of preparation method of chlorobenzene oxycarboxylic acid - Google Patents
A kind of preparation method of chlorobenzene oxycarboxylic acid Download PDFInfo
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- 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
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
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Abstract
The present invention provides a kind of preparation methods of chlorobenzene oxycarboxylic acid, comprising the following steps: S1) benzene oxygen fatty alcohol is under the action of catalyst A and catalyst B and chlorinating agent carries out 2 and/or 4 selective chlorination reactions, obtain chlorobenzene oxygen fatty alcohol；The catalyst A is lewis acid；The catalyst B is thioether, thiazole, isothiazole, thiophene or their halo derivatives of C5~22；S2) chlorobenzene oxygen fat alcohol and water carries out catalytic oxidation with oxidant under the effect of the catalyst, obtains chlorobenzene oxycarboxylic acid.The present invention passes through the redesign to process route, fine screening to catalyst and chlorinating agent, effectively reduces energy consumption, improves chlorination selectivity while avoiding the loss of effective component, the content of gained chlorobenzene oxycarboxylic acid is up to 98.5% or more, and total recovery is up to 99% or more.
Description
Technical field
The present invention relates to herbicide preparation technical field more particularly to a kind of preparation methods of chlorobenzene oxycarboxylic acid.
Background technique
Currently, the preparation method of chlorobenzene oxycarboxylic acid mainly includes the following steps:
1) using phenol as primary raw material, chlorinated phenol is made through chlorination.The chlorinated phenol of this step output has the irritation of extremely difficult news
Smell causes production on-site environment very poor, and chlorination is selectively poor.
2) chlorinated phenol is condensed with chlorinated carboxylic acid under alkaline condition, and reaction solution is acidified, chlorobenzene oxygen carboxylic is obtained by filtration
Sour wet feed obtains chlorobenzene oxycarboxylic acid after drying.Dichlorophenol or multi-chlorophenol in this step chlorinated phenol are in the condensation process, it may occur that two
Intermolecular condensation generates the extremely toxic substance of extremely difficult degradation -- dioxin, and also contain two in the chlorobenzene oxycarboxylic acid produced
English is disliked, brings great risk to the health of environment and producers.
Above method chlorination poor selectivity, aftertreatment technology will cause loss of effective components, and the yield of product is relatively low.Simultaneously
Using phenol be raw material through chlorination, condensation synthesis chlorobenzene oxycarboxylic acid when, can output largely containing hydroxycarboxylic acid and abraum salt
Waste water, and the largely dangerous waste containing chlorinated phenol, chlorobenzene oxycarboxylic acid, three-protection design pressure is big, processing cost is high.
Summary of the invention
In view of this, having the technical problem to be solved in the present invention is that providing a kind of preparation method of chlorobenzene oxycarboxylic acid
There are higher yield and purity, and safety and environmental protection.
In order to solve the above technical problems, the present invention provides a kind of preparation methods of chlorobenzene oxycarboxylic acid, including following step
It is rapid:
S1) benzene oxygen fatty alcohol is under the action of catalyst A and catalyst B and chlorinating agent carries out 2 and/or 4 selections
Property chlorination reaction, obtains chlorobenzene oxygen fatty alcohol；
The catalyst A is lewis acid；
The catalyst B is thioether, thiazole, isothiazole, thiophene or their halo derivatives of C5~22；
S2) chlorobenzene oxygen fat alcohol and water carries out catalytic oxidation with oxidant under the effect of the catalyst, obtains
Chlorobenzene oxycarboxylic acid.
In the present invention, the benzene oxygen fatty alcohol has I~formula of following formula, IV any structure:
Wherein, R1The preferably alkylidene of C1~C3, further, preferably methylene (- CH2), methylmethylene (-
CH(CH3) -), ethylidene (- CH2-CH2) or propylidene (- CH2-CH2-CH2-)。
The catalyst A is lewis acid；Preferably SnCl4、MgCl2、FeCl3、AlCl3、BF3、ZnCl2、TiCl4、
SbF5、Al2O3、Fe2O3、TiO2、Pb(OAc)2、Zn(OAc)2And Al2O(OAc)4One of or it is a variety of；More preferably MgCl2、
FeCl3、ZnCl2、SbF5、TiO2With Pb (OAc)2One of or a variety of, further preferably FeCl3、TiO2With Pb (OAc)2In
It is one or more.
The catalyst B is thioether, thiazole, isothiazole, thiophene or their halo derivatives of C5~22；Preferably uncle
Butyl methyl thioether, tert-butylsulfide, diphenyl sulfide, 4,4 '-dichloro diphenyl sulfides, 2- methyl diphenyl sulfide, 2,4,6- trimethylbenzene sulphur
Ether, 4,4'- thiobis (6- tert-butyl -3- methylphenol), thiazole, 2- ethyl thiazole, 2,5- dichloro thiazole, 4- methylthiazol,
2- tertiary butyl thiazole, isothiazole, 4,5- dimethyl isothiazole, 5- chloroisothiazole, 2,4,5- tri-tert isothiazole, thiophene, 2-
One of methylthiophene, 2,5- thioxene, tri- chlorothiophene of 3- chlorothiophene, 3,4- dichloro-thiophene and 2,3,4- are a variety of；
More preferably 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 and 2,3,4-
One of three chlorothiophenes are a variety of；Further 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 dosage of the catalyst A is preferably the 0.05%~1.0% of benzene oxygen fatty alcohol weight, more preferably 0.25%~
1.0%, further preferably 0.5%~1.0%.
The dosage of the catalyst B is preferably the 0.05%~1.0% of benzene oxygen fatty alcohol weight, more preferably 0.2%~
0.8%, further preferably 0.3%~0.5%.
The dosage of the catalyst A is unsuitable very few, otherwise will lead to chlorination and selectively declines to a great extent, but dosage is excessive
It also will increase the difficulty of product separation other than uneconomical；The dosage of catalyst B is unsuitable very few, otherwise will lead to reaction and does not occur
Or reaction is slowly, excessively not only the uneconomical selectivity that also results in decreases dosage, while also will increase product separating difficulty.
The chlorinating agent can be the general chlorinating agent of phenol chlorination reaction, preferably chlorine, thionyl chloride or chlorosulfuric acid,
More preferably chlorine or chlorosulfuric acid.
Described 2 and/or 4 selective chlorination reactions, refer to 2 single substitution reactions, 4 single substitution reactions or 2
Position and 4 disubstituted reactions.
When selective chlorination reaction is in 2 or 4 progress single substitution reaction, as benzene oxygen fatty alcohol structure such as
Shown in I~formula of formula IV, the molar ratio of the benzene oxygen fatty alcohol and chlorinating agent is preferably 1:(0.99~1.2), more preferably 1:(1
~1.1), further preferably 1:(1.01~1.03).
When selective chlorination reaction is two substitution reaction, if the structure of benzene oxygen fatty alcohol is as shown in formula I, product is
The molar ratio of 2,4- Dichlorophenoxy fatty alcohols, the benzene oxygen fatty alcohol and chlorinating agent is preferably 1:(1.98~2.4), more preferably
1:(2~2.2), further preferably 1:(2.02~2.06).
The dosage of chlorinating agent is unsuitable very few, and otherwise can make raw material does not turn higher, but dosage excessively will lead to again it is more
Over-chlorinated products generation, to react it is unfavorable.
Preferably -20~100 DEG C of the temperature of the selective chlorination reaction, more preferably -20~60 DEG C, further preferably
It is -20~20 DEG C.
The reaction temperature can keep higher reactivity and chlorination selectivity simultaneously.
In some embodiments of the invention, prepared chloro-product structure is as follows:
The selective chlorination after reaction, is preferably evaporated under reduced pressure, and the fraction for collecting corresponding boiling range can be obtained
Chlorobenzene oxygen fatty alcohol.
Then chlorobenzene oxygen fat alcohol and water carries out catalytic oxidation with oxidant under the effect of the catalyst, obtains
Chlorobenzene oxycarboxylic acid.
Specifically, a certain proportion of catalyst and water is added into chlorobenzene oxygen fatty alcohol, under certain temperature and pressure
A certain proportion of oxidant is added and carries out catalytic oxidation, end of reaction heat filtering, filter cake is catalyst direct reuse, filtrate
15~20 DEG C of filterings are cooled to, chlorobenzene oxycarboxylic acid wet feed and mother liquor, chlorobenzene oxycarboxylic acid wet feed chlorobenzene oxygen obtained by drying are obtained
Carboxylic acid, mother liquor reuse.
The catalyst is preferably Sb2O5、MoO3、MnO2、Ag2O、Cu2O, molecular sieve, active carbon, platinum carbon or palladium carbon.It is used
The 1%~10% of amount preferably chlorobenzene oxygen fatty alcohol weight, more preferably 5%~10%.
The dosage of the water is not particularly limited, preferably 1~3 times of chlorobenzene oxygen fatty alcohol weight.Under the dosage, instead
Rate with higher is answered, and catalyst is easily recycled.
The oxidant is preferably the clean oxygen source such as air, oxygen or ozone, preferably oxygen.
The molar ratio of oxygen atom is preferably 1:(2.2~3 in the chlorobenzene oxygen fatty alcohol and oxidant), more preferably 1:
(2.2~2.6), further preferably 1:(2.2~2.4).
The temperature of the catalytic oxidation is preferably 60~140 DEG C, and more preferably 80~100 DEG C.The catalysis oxidation
The pressure of reaction is preferably 0.1~1.2MPa, more preferably 0.4~0.8MPa.
The temperature of the heat filtering is preferably 80~100 DEG C, more preferably 90~100 DEG C, further preferably 95~100
℃。
In some embodiments of the invention, obtained chlorobenzene oxycarboxylic acid structure is as follows:
The equation of corresponding catalytic oxidation is as follows:
Chlorobenzene oxycarboxylic acid prepared by the present invention can also be directly added into auxiliary agent and be made into respectively directly as herbicide products
Kind herbicide formulations.
Compared with prior art, the present invention provides a kind of preparation methods of chlorobenzene oxycarboxylic acid, comprising the following steps:
S1) benzene oxygen fatty alcohol is under the action of catalyst A and catalyst B and the selective chlorination of chlorinating agent progress 2 and/or 4 is anti-
It answers, obtains chlorobenzene oxygen fatty alcohol；The catalyst A is lewis acid；The catalyst B is the thioethers of C5~22, thiazole, different
Thiazole, thiophene or their halo derivatives；S2) chlorobenzene oxygen fat alcohol and water, under the effect of the catalyst with oxidant into
Row catalytic oxidation obtains chlorobenzene oxycarboxylic acid.
The present invention is using benzene oxygen fatty alcohol as raw material, and chosen property chlorination synthesizes chlorobenzene oxygen fatty alcohol, then catalysis oxidation
Chlorobenzene oxycarboxylic acid is obtained, compared with existing synthetic technology, process route has obtained great simplification, and effectively avoiding has
The production and use of the chlorinated phenol of bad smell, fundamentally prevented severe toxicity dioxin generation, while intermediate product and
Chlorinated phenol will not be contained in product, greatly improve the operating environment of product quality and production scene.
The waste water containing hydroxycarboxylic acid and metal chloride will not be not only generated in synthesis process and containing chlorinated phenol, chlorobenzene
The dangerous waste of oxycarboxylic acid also simplifies post-processing, has effectively prevented the generation of high COD, high-salt wastewater, significantly reduced at the three wastes
Reason amount, three-protection design difficulty and processing cost.
It is final of the invention by the redesign to process route, the fine screening to catalyst and chlorinating agent, by Louis
This acid and special catalyst are used in combination, and effectively reduce energy consumption, improve chlorination selectivity while avoiding effective component
Loss, the content of gained chlorobenzene oxycarboxylic acid is up to 98.5% or more, and total recovery is up to 99% or more.Compared with the prior art,
Effectively increase selectivity, improve product quality, prevented the output of high-salt wastewater, avoid chlorobenzene oxycarboxylic acid drying and
Dust harzard caused by use, has saved the energy, reduces equipment investment.
Detailed description of the invention
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of 2,4 dichlorophenoxyacetic acid obtained in the embodiment of the present invention 1.
Specific embodiment
In order to further illustrate the present invention, below with reference to embodiment to the preparation side of chlorobenzene oxycarboxylic acid provided by the invention
Method is described in detail.
Embodiment 1
The oxidation of Phenoxyethanol (1mol), 0.21g 99% of 139.58g 99% are sequentially added into 500mL four-hole bottle
The 2 of aluminium and 1.19g 99%, 4,5- tri-tert isothiazole, the chlorine of 154.69g 99% is passed through at -20 DEG C, has led to heat preservation
30min is reacted, 110~120 DEG C of fraction is distilled and collected under 1kpa pressure, 2,4- Dichlorophenoxy ethyl alcohol 207.89g is obtained, contains
Amount 99.1%, yield in terms of Phenoxyethanol 99.48%.
18.71g ZSM-5 molecular sieve is added into distillation gained 2,4- Dichlorophenoxy ethyl alcohol and makees catalyst, 415.8g is added
Water, being passed through 99.9% oxygen to pressure is 0.7MPa, is reacted at 130 DEG C, it is common enter 38.44g oxygen, end of reaction is in 90
DEG C filtering, filtrate is cooled to 15 DEG C, filters to obtain 2,4- dichlorphenoxyacetic acid wet feed, and wet feed is dried to obtain 2,4- dichlorphenoxyacetic acid
221.71g, content 98.8%, yield in terms of Phenoxyethanol 99.08%.
2,4- dichlorphenoxyacetic acid obtained in embodiment 1 is analyzed using nuclear magnetic resonance, obtains its nuclear magnetic resonance
Hydrogen spectrogram (1HNMR (DMSO-d6)), as shown in Figure 1.
Comparative example 1
The oxidation of Phenoxyethanol (1mol), 0.21g 99% of 139.58g 99% are sequentially added into 500mL four-hole bottle
Aluminium is passed through the chlorine of 154.69g 99% at -20 DEG C, has led to insulation reaction 30min, distills and collects under 1kpa pressure
110~120 DEG C of fraction obtains 2,4- Dichlorophenoxy ethyl alcohol 187.22g, and content 98.7%, yield is in terms of Phenoxyethanol
89.23%.
16.76g ZSM-5 molecular sieve is added into distillation gained 2,4- Dichlorophenoxy ethyl alcohol and makees catalyst, is added
372.97g water, being passed through 99.9% oxygen to pressure is 0.7MPa, is reacted at 130 DEG C, it is common enter 34.48g oxygen, reaction
It finishes and is filtered in 90 DEG C, filtrate is cooled to 15 DEG C, filters to obtain 2,4- dichlorphenoxyacetic acid wet feed, and wet feed is dried to obtain 2,4- dichloro
Phenoxy acetic acid 198.28g, content 98.2%, yield in terms of Phenoxyethanol 88.07%.
Comparative example 2
Sequentially added into 500mL four-hole bottle the Phenoxyethanol (1mol) of 139.58g 99%, 1.19g 99% 2,4,
5- tri-tert isothiazole, is passed through the chlorine of 154.69g 99% at -20 DEG C, has led to insulation reaction 30min, in 1kpa pressure
The lower fraction distilled and collect 110~120 DEG C, obtains 2,4- Dichlorophenoxy ethyl alcohol 169.54g, content 98.6%, yield is with benzene oxygen
Alcohol meter 80.72%.
15.16g ZSM-5 molecular sieve is added into distillation gained 2,4- Dichlorophenoxy ethyl alcohol and makees catalyst, is added
337.38g water, being passed through 99.9% oxygen to pressure is 0.7MPa, is reacted at 130 DEG C, it is common enter 31.19g oxygen, reaction
It finishes and is filtered in 90 DEG C, filtrate is cooled to 15 DEG C, filters to obtain 2,4- dichlorphenoxyacetic acid wet feed, and wet feed is dried to obtain 2,4- dichloro
Phenoxy acetic acid 179.78g, content 98.1%, yield in terms of Phenoxyethanol 79.86%.
Embodiment 2
The chlorination of Phenoxyethanol (1mol), 0.77g 99% of 139.58g 99% are sequentially added into 500mL four-hole bottle
The 4 of magnesium and 0.35g 99%, 4 '-dichloro diphenyl sulfides, are added dropwise to the chlorosulfuric acid of 137.70g 99% at 30 DEG C, and it is anti-to drip off heat preservation
30min is answered, 105~115 DEG C of fraction is distilled and collected under 1kpa pressure, obtains 4- chlorophenoxyethanol 173.31g, content
98.8%, yield in terms of Phenoxyethanol 99.24%.
10.40g MoO is added into distillation gained 4- chlorophenoxyethanol3Make catalyst, 390.0g water is added, is passed through
99.9% oxygen to pressure be 0.1MPa, reacted at 80 DEG C, it is common enter 36.84g oxygen, end of reaction in 80 DEG C filter,
Filtrate is cooled to 15 DEG C, filters to obtain 4-chlorophenoxyacetic acid wet feed, and wet feed is dried to obtain 4-chlorophenoxyacetic acid 187.16g, content
98.5%, yield in terms of Phenoxyethanol 98.84%.
Embodiment 3
The chlorination of benzene oxygen butanol (1mol), 0.08g 99% of 167.92g 99% are sequentially added into 500mL four-hole bottle
3, the 4- dichloro-thiophene of zinc and 1.26g 99%, is passed through the chlorine of 157.56g 99% at 0 DEG C, has led to insulation reaction 30min,
The fraction that 120~130 DEG C are distilled and collected under 1kpa pressure, obtains 2,4- Dichlorophenoxy butanol 236.06g, content 98.9%,
Yield is 99.34% in terms of benzene oxygen butanol.
16.52g carbon compositing catalyst is added into distillation gained 2,4- Dichlorophenoxy butanol, 236.1g water is added, leads to
Enter air to pressure be 1.2MPa, reacted at 60 DEG C, it is common enter 220.95g air, end of reaction in 95 DEG C filter, filtrate drop
Temperature filters to obtain 2,4- Dichlorophenoxybutanoic wet feed to 15 DEG C, and wet feed is dried to obtain 2,4- Dichlorophenoxybutanoic 249.85g, content
98.6%, yield is 98.94% in terms of benzene oxygen butanol.
Embodiment 4
2- phenoxy group -1- propyl alcohol (1mol), the 0.54g 99% of 153.75g 99% are sequentially added into 500mL four-hole bottle
Iron oxide and 1.00g 99% 4,4 '-thiobis (6- tert-butyl -3- methylphenol), be passed through 85.94g at 50 DEG C
99% chlorine has led to insulation reaction 30min, and 110~120 DEG C of fraction is distilled and collected under 1kpa pressure, obtains 2- (4- chlorine
Phenoxy group) -1- propyl alcohol 187.40g, content 99.1%, yield is 99.49% in terms of 2- phenoxy group -1- propyl alcohol.
14.99g Sb is added into distillation gained 2- (4- chlorophenoxy) -1- propyl alcohol2O5Make catalyst, 562.2g is added
Water, being passed through 99.9% oxygen to pressure is 0.8MPa, is reacted at 120 DEG C, it is common enter 40.04g oxygen, end of reaction in
100 DEG C of filterings, filtrate are cooled to 15 DEG C, filter to obtain 2- (4- chlorophenoxy) propionic acid wet feed, and wet feed is dried to obtain 2- (4- chlorobenzene oxygen
Base) propionic acid 201.23g, content 98.8%, yield is 99.09% in terms of 2- phenoxy group -1- propyl alcohol.
Embodiment 5
Sequentially added into 500mL four-hole bottle the 2- chlorobenzene oxygen butanol (1mol) of 202.71g 99%, 0.51g99% four
2, the 5- dichloro thiazole of stannic chloride and 0.10g 99%, the chlorosulfuric acid of 140.42g 99% is added dropwise at 60 DEG C, drips off heat preservation
30min is reacted, 120~130 DEG C of fraction is distilled and collected under 1kpa pressure, 2,4- Dichlorophenoxy butanol 236.06g is obtained, contains
Amount 99.2%, yield is 99.58% in terms of 2- chlorobenzene oxygen butanol.
2.36g Pt/C is added into distillation gained 2,4- Dichlorophenoxy butanol and makees catalyst, 590.2g water is added, is passed through
Air to pressure be 1.1MPa, reacted at 80 DEG C, it is common enter 228.57g air, end of reaction in 85 DEG C filter, filtrate cooling
To 15 DEG C, 2,4- Dichlorophenoxybutanoic wet feed is filtered to obtain, wet feed is dried into obtain 2,4- Dichlorophenoxybutanoic 249.85g, content
98.9%, yield is 99.18% in terms of 2- chlorobenzene oxygen butanol.
Embodiment 6
2- phenoxy group -1- propyl alcohol (1mol), the 1.54g 99% of 153.75g 99% are sequentially added into 500mL four-hole bottle
Iron chloride and 1.54g 99% tertbutyl methyl thioether, the thionyl chloride of 237.92g 99% is added dropwise at 40 DEG C, drip
Complete insulation reaction 30min, distills under 1kpa pressure and collects 115~125 DEG C of fraction, obtains 2- (2,4- dichlorophenoxy)-
1- propyl alcohol 221.98g, content 99.0%, yield is 99.41% in terms of 2- phenoxy group -1- propyl alcohol.
11.10g Cu is added into distillation gained 2- (2,4- dichlorophenoxy) -1- propyl alcohol2O makees catalyst, is added
277.5g water, being passed through 99% ozone to pressure is 0.3MPa, is reacted at 90 DEG C, it is common enter 37.17g ozone, end of reaction
Filtered in 90 DEG C, filtrate is cooled to 15 DEG C, filters to obtain 2- (2,4- dichlorophenoxy) propionic acid wet feed, by wet feed dry 2- (2,
4- dichlorophenoxy) propionic acid 235.78g, content 98.7%, yield is 99.01% in terms of 2- phenoxy group -1- propyl alcohol.
Embodiment 7
Sequentially added into 500mL four-hole bottle 188.54g 99% 2- (4- chlorophenoxy) -1- propyl alcohol (1mol),
The titanium tetrachloride of 0.85g 99% and the tert-butylsulfide of 0.85g 99%, are passed through the chlorine of 85.94g 99% at 100 DEG C,
Lead to insulation reaction 30min, 115~125 DEG C of fraction is distilled and collected under 1kpa pressure, obtains 2- (2,4- Dichlorophenoxies
Base) -1- propyl alcohol 221.98g, content 98.8%, yield is 99.17% in terms of 2- (4- chlorophenoxy) -1- propyl alcohol.
8.88g MnO is added into distillation gained 2- (2,4- dichlorophenoxy) -1- propyl alcohol2Make catalyst, is added
610.4g water, being passed through 99.9% oxygen to pressure is 0.5MPa, is reacted at 100 DEG C, it is common enter 41.64g oxygen, reacted
Finish and filtered in 100 DEG C, filtrate is cooled to 15 DEG C, filters to obtain 2- (2,4- dichlorophenoxy) propionic acid wet feed, wet feed is dried to obtain 2-
(2,4- dichlorophenoxy) propionic acid 235.78g, content 98.5%, yield is 98.77% in terms of 2- (4- chlorophenoxy) -1- propyl alcohol.
Embodiment 8
The chlorination of Phenoxyethanol (1mol), 1.05g 99% of 139.58g 99% are sequentially added into 500mL four-hole bottle
The 2 of aluminium and 0.21g 99%, 4,6- trimethylbenzene thioethers, the chlorosulfuric acid of 275.39g 99% is added dropwise at 70 DEG C, has led to guarantor
Temperature reaction 30min, distills and is collected under 1kpa pressure 110~120 DEG C of fraction, obtain 2,4- Dichlorophenoxy ethyl alcohol 207.89g,
Content 98.9%, yield in terms of Phenoxyethanol 99.29%.
20.79g carbon compositing catalyst is added into distillation gained 2,4- Dichlorophenoxy ethyl alcohol, 363.8g water is added, leads to
Entering 99% ozone to pressure is 0.9MPa, is reacted at 140 DEG C, it is common enter 35.56g ozone, end of reaction filters in 95 DEG C,
Filtrate is cooled to 15 DEG C, filters to obtain 2,4- dichlorphenoxyacetic acid wet feed, and wet feed is dried to obtain 2,4- dichlorphenoxyacetic acid
221.71g, content 98.6%, yield in terms of Phenoxyethanol 98.89%.
Embodiment 9
2- methylenedioxy phenoxy ethyl alcohol (1mol), the 1.00g 99% of 153.75g 99% are sequentially added into 500mL four-hole bottle
Titanium dioxide and 0.85g 99% 2- ethyl thiazole, the chlorosulfuric acid of 140.42g 99% is added dropwise at 80 DEG C, has led to guarantor
Temperature reaction 30min, distills and is collected under 1kpa pressure 110~120 DEG C of fraction, obtain 4- chloro-2-methyl Phenoxyethanol
187.40g, content 99.1%, yield is with 2- methylenedioxy phenoxy alcohol meter 99.52%.
3.75g Pd/C is added into distillation gained 4- chloro-2-methyl Phenoxyethanol and makees catalyst, 374.8g water is added, leads to
Enter air to pressure be 1.0MPa, reacted at 70 DEG C, it is common enter 213.33g air, end of reaction in 85 DEG C filter, filtrate drop
Temperature filters to obtain methoxone wet feed to 15 DEG C, and wet feed is dried to obtain methoxone
201.23g, content 98.8%, yield is with 2- methylenedioxy phenoxy alcohol meter 99.12%.
Embodiment 10
2- methylenedioxy phenoxy butanol (1mol), the 1.55g 99% of 182.09g 99% are sequentially added into 500mL four-hole bottle
Lead acetate and 0.64g 99% 2,3,4- tri- chlorothiophenes, the thionyl chloride of 1118.96g 99% is added dropwise at 20 DEG C, lead to
Complete insulation reaction 30min, distills under 1kpa pressure and collects 120~130 DEG C of fraction, obtains 4- chloro-2-methyl benzene oxygen butanol
215.57g, content 99.3%, yield is 99.69% in terms of 2- methylenedioxy phenoxy butanol.
6.47g Ag is added into distillation gained 4- chloro-2-methyl benzene oxygen butanol2O makees catalyst, and 323.4g water is added, and leads to
Entering 99.9% oxygen to pressure is 0.6MPa, is reacted at 110 DEG C, it is common enter 43.24g air, end of reaction is in 95 DEG C of mistakes
Filter, filtrate are cooled to 15 DEG C, filter to obtain 4- chloro-2-methyl phenoxy butyric acid wet feed, and wet feed is dried to obtain 4- chloro-2-methyl benzene oxygen fourth
Sour 229.38g, content 99.0%, yield is 99.29% in terms of 2- methylenedioxy phenoxy butanol.
By above-described embodiment and comparative example it is found that preparation method provided by the invention yield with higher and purity.
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 (10)
1. a kind of preparation method of chlorobenzene oxycarboxylic acid, comprising the following steps:
S1) benzene oxygen fatty alcohol is under the action of catalyst A and catalyst B and chlorinating agent carries out 2 and/or 4 selective chlorine
Change reaction, obtains chlorobenzene oxygen fatty alcohol；
The catalyst A is lewis acid；
The catalyst B is thioether, thiazole, isothiazole, thiophene or their halo derivatives of C5~22；
S2) chlorobenzene oxygen fat alcohol and water carries out catalytic oxidation with oxidant under the effect of the catalyst, obtains chloro
Benzene oxycarboxylic acid.
2. preparation method according to claim 1, which is characterized in that the benzene oxygen fatty alcohol has I~formula of following formula IV
Any structure:
Wherein,
R1For the alkylidene of C1~C3.
3. preparation method according to claim 2, which is characterized in that the R1For-CH2,-CH (CH3)-,-(CH2)2-
Or-(CH2)3-。
4. preparation method according to claim 1, which is characterized in that the catalyst A is SnCl4、MgCl2、FeCl3、
AlCl3、BF3、ZnCl2、TiCl4、SbF5、Al2O3、Fe2O3、TiO2、Pb(OAc)2、Zn(OAc)2And Al2O(OAc)4One of
Or it is a variety of.
5. preparation method according to claim 1, which is characterized in that the catalyst B is tertbutyl methyl thioether, tertiary fourth
Base thioether, diphenyl sulfide, 4,4 '-dichloro diphenyl sulfides, 2- methyl diphenyl sulfide, 2,4,6- trimethylbenzene thioether, 4,4'- thiobis (6-
Tert-butyl -3- methylphenol), thiazole, 2- ethyl thiazole, 2,5- dichloro thiazole, 4- methylthiazol, 2- tertiary butyl thiazole, different thiophene
Azoles, 4,5- dimethyl isothiazole, 5- chloroisothiazole, 2,4,5- tri-tert isothiazole, thiophene, 2- methylthiophene, 2,5- diformazan
One of base thiophene, tri- chlorothiophene of 3- chlorothiophene, 3,4- dichloro-thiophene and 2,3,4- are a variety of.
6. preparation method according to claim 1, which is characterized in that the dosage of the catalyst A is benzene oxygen fatty alcohol weight
The 0.05%~1.0% of amount；The dosage of the catalyst B is the 0.05%~1.0% of benzene oxygen fatty alcohol weight.
7. preparation method according to claim 1, which is characterized in that the temperature of selective chlorination reaction is -20~
100℃；The temperature of the catalytic oxidation is 60~140 DEG C, and the pressure of the catalytic oxidation is 0.1~1.2MPa.
8. preparation method according to claim 1, which is characterized in that the step S2) in, catalyst Sb2O5、MoO3、
MnO2、Ag2O、Cu2O, molecular sieve, active carbon, platinum carbon, palladium carbon.
9. preparation method according to claim 1, which is characterized in that the step S2) in, oxidant is air, oxygen
Or ozone.
10. preparation method according to claim 1, which is characterized in that oxygen in the chlorobenzene oxygen fatty alcohol and oxidant
The molar ratio of atom is 1:(2.2~3).
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102180789A (en) * | 2011-03-25 | 2011-09-14 | 山东潍坊润丰化工有限公司 | Method for preparing aryloxycarboxylic acid technical |
| 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 |
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2018
- 2018-03-19 CN CN201810226615.4A patent/CN108947799A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102180789A (en) * | 2011-03-25 | 2011-09-14 | 山东潍坊润丰化工有限公司 | Method for preparing aryloxycarboxylic acid technical |
| 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 |
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