CN101429117A - Process for producing 2, 4, 6-trichlorobenzoic acid - Google Patents
Process for producing 2, 4, 6-trichlorobenzoic acid Download PDFInfo
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- CN101429117A CN101429117A CNA2008102396525A CN200810239652A CN101429117A CN 101429117 A CN101429117 A CN 101429117A CN A2008102396525 A CNA2008102396525 A CN A2008102396525A CN 200810239652 A CN200810239652 A CN 200810239652A CN 101429117 A CN101429117 A CN 101429117A
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Abstract
The invention relates to a method for preparing 2, 4, 6-trichloro-phenylacetic acid. Specifically, 1,3,5-trichloro-benzene and carbon tetrachloride react to generate 2,4,6-trichloro-benzotrichloride; the 2,4,6-trichloro-benzotrichloride and concentrated sulfuric acid react to prepare the 2,4,6-trichloro-phenylacetic acid; and finally, the 2,4,6-trichloro-phenylacetic acid is formed by refining and crystallization. The preparation method has the advantages of low cost, simple reaction steps, easy control of reaction conditions and the like.
Description
Technical field
The present invention relates to a kind ofly 2,4, the preparation method of 6-trichlorobenzoic acid is specifically related to a kind ofly pass through 1,3, and 5-trichloro-benzene and tetracol phenixin produce 2,4, the method for 6-trichlorobenzoic acid.
Background technology
2,4, the 6-trichlorobenzoic acid is a kind of important medicine intermediate, and available its made immunosuppressor and made the susceptibility reagent that is used to analyze the leukemia anticarcinogen.
Reported multiple Synthetic 2 in the prior art, 4, the method for 6-trichlorobenzoic acid, these methods are to be that raw material prepares 2,4 with the trichlorobenzene that replaces basically, the 6-trichlorobenzoic acid.
Patent ZL200410073917.0 discloses a kind of with 1,3, and the 5-trichloro-benzene is that raw material prepares 2,4, the method for 6-trichlorobenzoic acid through paying the gram acylation reaction.This method is passed through 1,3, and 5-trichloro-benzene and acylating reagent make 1-alkyl carbonyl-2,4, the 6-trichloro-benzene through paying a gram acylation reaction; its oxidizing reaction is made 2,4,6-trichlorobenzoic acid salt, will make at last 2; 4,6-trichlorobenzoic acid salt makes 2,4 through acidification reaction, the 6-trichlorobenzoic acid.Acylating reagent adopts Acetyl Chloride 98Min., propionyl chloride, butyryl chloride etc.The advantage of this invention is that preparation process is simple, but defective is that the acylating reagent price is higher, causes 2,4 of this invention production, and the 6-trichlorobenzoic acid does not possess advantage in price.
Summary of the invention
It is simple to the objective of the invention is to propose a kind of preparation process, cost low 2,4, the preparation method of 6-trichlorobenzoic acid.
The technical solution used in the present invention is:
Of the present invention 2,4, the preparation method of 6-trichloro-benzoyl chloride comprises following 4 steps:
(1) 1,3,5-trichloro-benzene and tetracol phenixin are under the catalysis of aluminum trichloride (anhydrous), 73～80 ℃ were reacted 1,3 5～10 hours, the weight ratio that 5-trichloro-benzene, tetracol phenixin and aluminum trichloride (anhydrous) are added is 0.9～1:2.8～3.2:0.9～1.2, generate 2,4,6-three chloro trichlorotoluene zotrichlorides;
(2) 2,4,120～130 ℃ of the 6-three chloro trichlorotoluene zotrichlorides and vitriol oils reaction 2～4 hours, the weight of the vitriol oil that is added is 1,3,7.5～8.5 times of 5-trichloro-benzene weight; Generate 2,4,6-trichlorobenzoic acid crude product;
(3) 2,4,6-trichlorobenzoic acid crude product refining;
(4) crystallization.
Wherein, of the present invention 2,4, the preparation method's of 6-trichloro-benzoyl chloride reactions steps and condition optimization are:
(1) in reactor, adds 1,3,5-trichloro-benzene and tetracol phenixin, add aluminum trichloride (anhydrous) behind the mixing, 75～78 ℃ of back flow reaction 8～10 hours, 1,3, the weight ratio that 5-trichloro-benzene, tetracol phenixin and aluminum trichloride (anhydrous) are added is 1:2.8～3.0:1～1.1; Be cooled to 30～50 ℃, add water and stir, separate lower floor's organism, reclaim the tetracol phenixin in the organism, get 2,4,6-three chloro trichlorotoluene zotrichloride crude products.
(2) in reactor, add the entry and the vitriol oil successively, be warming up to 120～130 ℃, add that step 1) makes 2,4,6-three chloro trichlorotoluene zotrichloride crude products, the weight of the water that is added is 1,3,1～1.5 times of 5-trichloro-benzene weight, the weight of the vitriol oil that is added is 1,3,8.0～8.5 times of 5-trichloro-benzene weight; After adding, 120～130 ℃ are incubated 3～6 hours; Reduce to the normal temperature crystallization, filter, wash, dry 2,4,6-trichlorobenzoic acid crude product.
(3) add in reactor that entry and step (two) make 2,4,6-trichlorobenzoic acid crude product, the interpolation mass percent concentration is 40% sodium hydroxide, and the pH value is adjusted to 10～14, the water that is added, 40% sodium hydroxide and 2,4, the weight ratio of 6-trichlorobenzoic acid crude product is: 2～4:0.4～0.6:1 adds gac, 70～100 ℃ kept 1～2 hour, and heat filtering is removed gac; Adjust the temperature to 40～65 ℃ after the filtration, the pH value be adjusted to 1～2, filter 2,4,6-trichlorobenzoic acid solid is also dry.
(4) step (three) is obtained 2,4,6-trichlorobenzoic acid solid adds Glacial acetic acid and water, added 2,4, the weight ratio of 6-trichlorobenzoic acid solid, Glacial acetic acid and water is 1:0.9～1.1:0.9～1.1, add gac, heating also kept heat filtering, crystallisation by cooling 0.5～1 hour in 80～90 ℃, filter, obtain 2,4,6-trichlorobenzoic acid crystal.
Wherein, reactions steps of the present invention and condition are more preferably:
(1) in reactor, adds 1,3,5-trichloro-benzene and tetracol phenixin, add aluminum trichloride (anhydrous) behind the mixing, 75～77 ℃ of back flow reaction 8～10 hours, 1,3, the weight ratio that 5-trichloro-benzene, tetracol phenixin and aluminum trichloride (anhydrous) are added is 1:2.8～3.0:1～1.1; Be cooled to 35～45 ℃, adding weight is 1,3, and 3～5 times water of 5-trichloro-benzene stirred 0.5～1.5 hour, separates lower floor's organism; With organism with the steam heating of 0.3MPa pressure 15～45 minutes, reclaim behind the tetracol phenixin 2,4,6-three chloro trichlorotoluene zotrichloride crude products.
The tetracol phenixin of this step can reuse after reclaiming, and the hydrogen chloride gas body and function acid proof pump that reaction process produces is extracted out and water absorbs.
(2) in reactor, add entry, add the vitriol oil again, be warming up to 125～130 ℃, by 1.0～1.6 liters/minute speed add that step 1) make 2,4,6-three chloro trichlorotoluene zotrichloride crude products, the weight of the water that is added is 1,3,1～1.2 times of 5-trichloro-benzene weight, the weight of the vitriol oil that is added is 1,3,8.0～8.5 times of 5-trichloro-benzene weight; After adding, 125～130 ℃ are incubated 3～4 hours; Reduce to normal temperature, crystallization is filtered, washing, dry 2,4,6-trichlorobenzoic acid crude product.
(3) add in reactor that entry and step (two) make 2,4,6-trichlorobenzoic acid crude product, the interpolation mass percent is 40% sodium hydroxide, the pH value is adjusted to 10～12, the water that is added, sodium hydroxide and 2,4, the weight ratio of 6-trichlorobenzoic acid crude product is: 3～4:0.45～0.55:1; Adding weight again is 2,4, the gac of 6-trichlorobenzoic acid crude product 1～5%, and 80～100 ℃ kept 1～2 hour, and heat filtering is removed gac; Adjust the temperature to 50～65 ℃ after the filtration, the pH value be adjusted to 1, be cooled to room temperature, filter 2,4,6-trichlorobenzoic acid solid is also dry.
(4) step (three) is obtained 2,4,6-trichlorobenzoic acid solid adds Glacial acetic acid and water, added 2,4, the weight ratio of 6-trichlorobenzoic acid solid, Glacial acetic acid and water is 1:1:1, adding weight is 2,4, the gac of 6-trichlorobenzoic acid solid 1～5%, heating also kept heat filtering, crystallisation by cooling 0.5～1 hour in 80～90 ℃, filter, obtain 2,4,6-trichlorobenzoic acid crystal.
The present invention is raw materials used to be commercially available technical pure reagent, and wherein the vitriol oil is a concentration greater than 95% the industrial vitriol oil, and Glacial acetic acid is a concentration greater than 99% industrial Glacial acetic acid.
The technical superiority that the present invention had is:
(1) preparation process of the present invention is simple, and reaction conditions is easy to control, and is not high to equipment requirements, is applicable to large-scale industrial production;
(2) production cost of the present invention is low because raw materials for production tetracol phenixin price is very low, but and recirculation utilization in reaction, so according to the preparation method of invention produce 2,4, the 6-trichlorobenzoic acid has very strong price advantage;
(3) 2,4 of preparation method's production of the present invention, the purity height of 6-trichlorobenzoic acid reaches 99.5% according to gas chromatographic analysis;
(4) productive rate height of the present invention, preparation method's of the present invention by product is few, and productive rate can reach 75%.
Embodiment
In order further to understand the present invention, the following examples only are used for further specifying the present invention, but and do not mean that any limitation of the invention.
Embodiment 1:
1, by 1,3,5-trichloro-benzene and carbon tetrachloride reaction, preparation 2,4,6-three chloro trichlorotoluene zotrichlorides:
In the enamel still of 1000L, drop into 100kg 1,3 successively, 5-trichloro-benzene, the 280kg tetracol phenixin stirred 10 minutes, added the 100kg aluminum trichloride (anhydrous), and 77 ℃ of reflux 8 hours are emitted a large amount of hydrogen chloride gas body and function water and are absorbed.
Be cooled to 30 ℃, with reaction mass slowly suction another have in the 2000L reactor of 300kg water, stirred 1.5 hours, tell lower floor's organism, with organism with the washing of 2 times of volumes 2 times; Again with organic layer with the steam heating of 0.3MPa pressure 25 minutes, do not go out for this reason to tetracol phenixin, reclaim behind the tetracol phenixin 2,4,6-three chloro trichlorotoluene zotrichloride crude products.
2, by 2,4,6-three chloro trichlorotoluene zotrichlorides and sulfuric acid reaction preparation 2,4, the 6-trichlorobenzoic acid:
Add 100kg water in the 2000L enamel still, slowly add the 750kg vitriol oil while stirring, be warming up to 125 ℃, keep this temperature, slowly add make in the step 12,4,6-three chloro trichlorotoluene zotrichloride crude products added in 50 minutes; Add back insulation 4 hours; Reduce to normal temperature, leach crystallization, with 2 times 2,4, the washing of 6-three chloro trichlorotoluene zotrichloride crude product volumes 1 time, dry 2,4,6-trichlorobenzoic acid crude product 87.6kg.The acid solution reusable edible.
3,2,4,6-trichlorobenzoic acid crude product refining:
Add 175.2kg water in the 2000L still, 87.6kg2,4,6-trichlorobenzoic acid crude product transfers to pH=10 with the sodium hydroxide of 35.04kg40%, adds the 0.9kg gac again, is warming up to 70 ℃ of maintenances 2 hours, and heat filtering is removed gac; Reduce to 50 ℃, be acidified to pH=1 with industrial concentrated hydrochloric acid, cooling is filtered, and drying gets 2,4,6-trichlorobenzoic acid solid 85kg.mp：162—164.3℃。
4, crystallization
In the still of 1000L, the 85kg crude product is added 85kg Glacial acetic acid, 85kg water, 0.85kg gac, heating also kept 1 hour in 90 ℃, heat filtering, crystallisation by cooling, filter 2,4,6-trichlorobenzoic acid 69.5kg, productive rate are 70%.Mp:160.9-161.7 ℃, use gas chromatographic analysis, purity is 99.5%.
Embodiment 2:
1, by 1,3,5-trichloro-benzene and carbon tetrachloride reaction, preparation 2,4,6-three chloro trichlorotoluene zotrichlorides:
In the enamel still of 1000L, drop into 274kg1 successively, 3,5-trichloro-benzene, the 810kg tetracol phenixin stirred 10 minutes, added the 300kg aluminum trichloride (anhydrous), and 80 ℃ of reflux 10 hours are emitted a large amount of hydrogen chloride gas body and function water and are absorbed.Be cooled to 40 ℃, with reaction mass slowly suction another have in the 2000L reactor of 1000kg water, stir half an hour, tell lower floor's organism, with organism with the washing of 2 times of volumes 2 times; Again with organic layer with the steam heating of 0.3MPa pressure 45 minutes, do not go out for this reason to tetracol phenixin, reclaim behind the tetracol phenixin 2,4,6-three chloro trichlorotoluene zotrichloride crude product 250kg.
2, by 2,4,6-three chloro trichlorotoluene zotrichlorides and sulfuric acid reaction preparation 2,4, the 6-trichlorobenzoic acid:
Add 300kg water in the 2000L enamel still, slowly add the 2208kg vitriol oil while stirring, be warming up to 125 ℃, keep this temperature, slowly add make in the step 12,4,6-three chloro trichlorotoluene zotrichloride crude product 250L divide to add in 3 hours.Add back insulation 3 hours.Reduce to normal temperature, leach crystallization, with the washing of 2 times of volumes 2 times, dry 2,4,6-trichlorobenzoic acid crude product 240kg.The acid solution reusable edible.
3,2,4,6-trichlorobenzoic acid crude product refining:
Add 800kg water in the 2000L still, 240kg2,4,6-trichlorobenzoic acid crude product transfers to pH=10 with the sodium hydroxide of 120kg40%, adds the 2kg gac again, is warming up to 90 ℃ of maintenances 1 hour, and heat filtering is removed gac; Reduce to 60 ℃, be acidified to pH=1, cooling, filter 2,4,6-trichlorobenzoic acid solid and dry 233kg.mp：162—164.3℃。
4, crystallization
In the still of 1000L, the 233kg crude product is added 233kg acetic acid, 233kg water, the 3kg gac heats and in 0.5 hour heat filtering of 90 ℃ of maintenances, cooling, crystallization get dry product 190kg, productive rate 56%.Mp:160.9-161.7 ℃, use the high resolution gas chromatography analysis, purity is 99.6%.
Embodiment 3
1. add 1,3 in reactor, 5-trichloro-benzene and tetracol phenixin add aluminum trichloride (anhydrous) behind the mixing, 75 ℃ of back flow reaction 12 hours, and 1,3, the weight ratio that 5-trichloro-benzene, tetracol phenixin and aluminum trichloride (anhydrous) are added is 1:3.0:1.1; Be cooled to 45 ℃, adding weight is 1,3, and 5 times water of 5-trichloro-benzene stirred 1.5 hours, separates lower floor's organism; With organism in the steam heating of 0.3MPa pressure 45 minutes, reclaim behind the tetracol phenixin 2,4,6-three chloro trichlorotoluene zotrichloride crude products.The tetracol phenixin of this step can reuse after reclaiming, and the hydrogen chloride gas body and function acid proof pump that reaction process produces is extracted out and water absorbs.
2. in reactor, add entry, add the vitriol oil again, be warming up to 130 ℃, by 1.6 liters/minute speed add that steps 1 make 2,4,6-three chloro trichlorotoluene zotrichloride crude products, adding weight is 1,3, the water that the weight of 5-trichloro-benzene is 1 times, adding weight is 1,3, the vitriol oil that 5-trichloro-benzene weight is 8.5 times; After adding, 125 ℃ are incubated 3 hours; Reduce to normal temperature, crystallization is filtered, washing, dry 2,4,6-trichlorobenzoic acid crude product.
3. add in reactor that entry and step 2 make 2,4,6-trichlorobenzoic acid crude product, the interpolation mass percent is 40% sodium hydroxide, the pH value is adjusted to 12, the water that is added, sodium hydroxide and 2,4, the weight ratio of 6-trichlorobenzoic acid crude product is: 3:0.45:1; Adding weight again is 2,4, the gac of 6-trichlorobenzoic acid crude product 5%, and 100 ℃ kept 1 hour, and heat filtering is removed gac; Adjust the temperature to 50 ℃ after the filtration, the pH value be adjusted to 1, be cooled to room temperature, filter 2,4,6-trichlorobenzoic acid solid is also dry.
4. step 3 is obtained 2,4,6-trichlorobenzoic acid solid adds Glacial acetic acid and water, added 2,4, the weight ratio of 6-trichlorobenzoic acid solid, Glacial acetic acid and water is 1:1:1, adding weight is 2,4, the gac of 6-trichlorobenzoic acid solid 5%, dissolving, heat filtering, cooling, crystallization obtains 2,4,6-trichlorobenzoic acid crystal.Mp:160.9-161.7 ℃, use the high resolution gas chromatography analysis, purity is 99.6%.
Embodiment 4
1. add 1,3 in reactor, 5-trichloro-benzene and tetracol phenixin add aluminum trichloride (anhydrous) behind the mixing, 78 ℃ of back flow reaction 8 hours, and 1,3, the weight ratio that 5-trichloro-benzene, tetracol phenixin and aluminum trichloride (anhydrous) are added is 1:2.8:1.1; Be cooled to 35 ℃, adding weight is 1,3, and 3 times water of 5-trichloro-benzene stirred 0.5 hour, separates lower floor's organism; With organism with the steam heating of 0.3MPa pressure 15 minutes, reclaim behind the tetracol phenixin 2,4,6-three chloro trichlorotoluene zotrichloride crude products.The tetracol phenixin of this step can reuse after reclaiming, and the hydrogen chloride gas body and function acid proof pump that reaction process produces is extracted out and water absorbs.
2. in reactor, add entry, add the vitriol oil again, be warming up to 130 ℃, by 1.0 liters/minute speed add that steps 1 make 2,4,6-three chloro trichlorotoluene zotrichloride crude products, adding weight is 1,3, the water that the weight of 5-trichloro-benzene is 1.2 times, adding weight is 1,3, the vitriol oil that 5-trichloro-benzene weight is 8 times; After adding, 125 ℃ are incubated 6 hours; Reduce to normal temperature, crystallization is filtered, washing, dry 2,4,6-trichlorobenzoic acid crude product.
3. add in reactor that entry and step 2 make 2,4,6-trichlorobenzoic acid crude product, the interpolation mass percent is 40% sodium hydroxide, the Ph value is adjusted to 12, the water that is added, sodium hydroxide and 2,4, the weight ratio of 6-trichlorobenzoic acid crude product is 4:0.55:1; Adding weight again is 2,4, the gac of 6-trichlorobenzoic acid crude product 1%, and 100 ℃ kept heat filtering 2 hours; Adjust the temperature to 65 ℃ after the filtration, the Ph value be adjusted to 1, be cooled to room temperature, filter 2,4,6-trichlorobenzoic acid solid is also dry.
4. step 3 is obtained 2,4,6-trichlorobenzoic acid solid adds Glacial acetic acid and water, added 2,4, the weight ratio of 6-trichlorobenzoic acid solid, Glacial acetic acid and water is 1:1:1, adding weight is 2,4, the gac of 6-trichlorobenzoic acid solid 5%, heating also kept 0.5 hour in 90 ℃, heat filtering is removed gac, cooling, and crystallization obtains 2,4,6-trichlorobenzoic acid crystal.Mp:160.9-161.7 ℃, use the high resolution gas chromatography analysis, purity is 99.5%.
Embodiment 5
1. add 1,3 in reactor, 5-trichloro-benzene and tetracol phenixin add aluminum trichloride (anhydrous) behind the mixing, 76 ℃ of back flow reaction 9 hours, and 1,3, the weight ratio that 5-trichloro-benzene, tetracol phenixin and aluminum trichloride (anhydrous) are added is 1:2.9:1; Be cooled to 50 ℃, add water and stir, separate lower floor's organism, reclaim the tetracol phenixin in the organism, get 2,4,6-three chloro trichlorotoluene zotrichloride crude products.
2. in reactor, add the entry and the vitriol oil successively, be warming up to 125 ℃, add that step 1 makes 2,4,6-three chloro trichlorotoluene zotrichloride crude products, adding weight is 1,3, the water that 5-trichloro-benzene weight is 1.2 times, adding weight is 1,3, the vitriol oil that 5-trichloro-benzene weight is 8 times; After adding, 125 ℃ are incubated 5 hours; Reduce to normal temperature, crystallization is filtered, wash, dry 2,4,6-trichlorobenzoic acid crude product.
3. add in reactor that entry and step 2 make 2,4,6-trichlorobenzoic acid crude product, the interpolation mass percent concentration is 40% sodium hydroxide, the pH value is adjusted to 14, the water that is added, sodium hydroxide and 2,4, the weight ratio of 6-trichlorobenzoic acid crude product is 4:0.6:1, adding weight is 2,4,6-trichlorobenzoic acid crude product 2% gac, 80 ℃ kept 1.5 hours, and heat filtering is removed gac; Adjust the temperature to 40 ℃ after the filtration, the pH value be adjusted to 2, filter 2,4,6-trichlorobenzoic acid solid is also dry.
5. step (three) is obtained 2,4,6-trichlorobenzoic acid solid adds Glacial acetic acid and water, added 2,4, the weight ratio of 6-trichlorobenzoic acid solid, Glacial acetic acid and water is 1:0.9:0.9, adding weight is 2,4, the gac of 6-trichlorobenzoic acid solid 1%, heating also kept 1 hour in 90 ℃, heat filtering, cooling, crystallization obtains 2,4,6-trichlorobenzoic acid crystal.Mp:160.9-161.7 ℃, use the high resolution gas chromatography analysis, purity is 99.6%.
Embodiment 6
1. add 1,3 in reactor, 5-trichloro-benzene and tetracol phenixin add aluminum trichloride (anhydrous) behind the mixing, 76 ℃ of back flow reaction 9 hours, and 1,3, the weight ratio that 5-trichloro-benzene, tetracol phenixin and aluminum trichloride (anhydrous) are added is 1:3.0:1.1; Be cooled to 45 ℃, add water and stir, separate lower floor's organism, reclaim the tetracol phenixin in the organism, get 2,4,6-three chloro trichlorotoluene zotrichloride crude products.
2. in reactor, add the entry and the vitriol oil successively, be warming up to 120～130 ℃, add that step 1 makes 2,4,6-three chloro trichlorotoluene zotrichloride crude products, adding weight is 1,3, the water that the weight of 5-trichloro-benzene is 1.3 times, adding weight is 1,3, the vitriol oil that the weight of 5-trichloro-benzene is 8 times; After adding, 120 ℃ are incubated 3 hours; Reduce to normal temperature, crystallization is filtered, wash, dry 2,4,6-trichlorobenzoic acid crude product.
3. add in reactor that entry and step 2 make 2,4,6-trichlorobenzoic acid crude product, the interpolation mass percent concentration is 40% sodium hydroxide, the pH value is adjusted to 11, the water that is added, sodium hydroxide and 2,4, the weight ratio of 6-trichlorobenzoic acid crude product is 3:0.5:1, adding weight is 2,4,6-trichlorobenzoic acid crude product 3% gac, 90 ℃ kept heat filtering 1.5 hours; Adjust the temperature to 65 ℃ after the filtration, the pH value be adjusted to 2, filter 2,4,6-trichlorobenzoic acid solid is also dry.
4. step 3 is obtained 2,4,6-trichlorobenzoic acid solid adds Glacial acetic acid and water, added 2,4, the weight ratio of 6-trichlorobenzoic acid solid, Glacial acetic acid and water is 1:1.1:1.1, adding weight is 2,4, the gac of 6-trichlorobenzoic acid solid 3%, heating also kept 1 hour in 90 ℃, heat filtering is removed gac, cooling, and crystallization obtains 2,4,6-trichlorobenzoic acid crystal.Mp:160.9-161.7 ℃, use the high resolution gas chromatography analysis, purity is 99.5%.
Claims (9)
1. one kind 2,4, the preparation method of 6-trichlorobenzoic acid is characterized in that comprising following four steps:
1) 1,3,5-trichloro-benzene and tetracol phenixin are under the catalysis of aluminum trichloride (anhydrous), and 73～80 ℃ were reacted 5～10 hours, 1,3, the weight ratio that 5-trichloro-benzene, tetracol phenixin and aluminum trichloride (anhydrous) are added is 0.9～1:2.8～3.2:0.9～1.2, generate 2,4,6-three chloro trichlorotoluene zotrichlorides;
2) 2,4,120～135 ℃ of the 6-three chloro trichlorotoluene zotrichlorides and vitriol oils reaction 3～6 hours, the weight of the vitriol oil that is added is 1,3,7.5～8.5 times of 5-trichloro-benzene weight; Generate 2,4,6-trichlorobenzoic acid crude product;
3) 2,4,6-trichlorobenzoic acid crude product refining;
4) crystallization.
One kind as claimed in claim 12,4, the preparation method of 6-trichlorobenzoic acid is characterized in that: prepare 2,4 in the step 1), the step of 6-three chloro trichlorotoluene zotrichlorides is:
In reactor, add 1,3,5-trichloro-benzene and tetracol phenixin, add aluminum trichloride (anhydrous) behind the mixing, 75～78 ℃ of back flow reaction 8～12 hours, 1,3, the weight ratio that 5-trichloro-benzene, tetracol phenixin and aluminum trichloride (anhydrous) are added is 1:2.8～3.0:1～1.1; Be cooled to 30～50 ℃, add water and stir, separate lower floor's organism, reclaim the tetracol phenixin in the organism, get 2,4,6-three chloro trichlorotoluene zotrichloride crude products.
One kind as claimed in claim 22,4, the preparation method of 6-trichlorobenzoic acid is characterized in that:
Prepare 2,4 in the step 1), the step of 6-three chloro trichlorotoluene zotrichlorides is:
In reactor, add 1,3,5-trichloro-benzene and tetracol phenixin, add aluminum trichloride (anhydrous) behind the mixing, 75～78 ℃ of back flow reaction 8～12 hours, 1,3, the weight ratio that 5-trichloro-benzene, tetracol phenixin and aluminum trichloride (anhydrous) add is 1:2.8～3.0:1～1.1; Be cooled to 35～45 ℃, adding weight is 1,3, and 3～5 times water of 5-trichloro-benzene stirred 0.5～1.5 hour, separates lower floor's organism; With organism with the steam heating of 0.3MPa pressure 15～45 minutes, reclaim behind the tetracol phenixin 2,4,6-three chloro trichlorotoluene zotrichloride crude products.
One kind as claimed in claim 12,4, the preparation method of 6-trichlorobenzoic acid is characterized in that:
Step 2) preparation 2,4 in, the step of 6-trichlorobenzoic acid is:
In reactor, add the entry and the vitriol oil successively, be warming up to 120～130 ℃, add that step 1) makes 2,4,6-three chloro trichlorotoluene zotrichloride crude products, the weight of the water that is added is 1,3,1～1.5 times of 5-trichloro-benzene weight, the weight of the vitriol oil that is added is 1,3,8～8.5 times of 5-trichloro-benzene weight; After adding, 120～130 ℃ are incubated 3～6 hours; Reduce to normal temperature, crystallization is filtered, washing, dry 2,4,6-trichlorobenzoic acid crude product.
One kind as claimed in claim 42,4, the preparation method of 6-trichlorobenzoic acid is characterized in that:
Step 2) preparation 2,4 in, the step of 6-trichlorobenzoic acid is:
In reactor, add entry, add the vitriol oil again, be warming up to 125～130 ℃, by 1.0～1.6 liters/minute speed add that step 1) make 2,4,6-three chloro trichlorotoluene zotrichloride crude products, the weight of the water that is added is 1,3,1～1.2 times of 5-trichloro-benzene weight, the weight of the vitriol oil that is added is 1,3,8～8.5 times of 5-trichloro-benzene weight; After adding, 125～130 ℃ are incubated 3～4 hours; Reduce to normal temperature, the washing, dry 2,4,6-trichlorobenzoic acid crude product.
One kind as claimed in claim 12,4, the preparation method of 6-trichlorobenzoic acid is characterized in that:
In the step 3) 2,4, the step of 6-trichlorobenzoic acid crude product refining is:
In reactor, add entry and step 2) make 2,4,6-trichlorobenzoic acid crude product, the interpolation mass percent concentration is 40% sodium hydroxide, and the Ph value is adjusted to 10～14, the water that is added, 40% sodium hydroxide and 2,4, the weight ratio of 6-trichlorobenzoic acid crude product is: 2～4:0.4～0.6:1 adds gac, 70～100 ℃ kept 1～2 hour, and heat filtering is removed gac; Adjust the temperature to 40～65 ℃ after the filtration, the pH value be adjusted to 1～2, filter 2,4,6-trichlorobenzoic acid solid is also dry.
One kind as claimed in claim 62,4, the preparation method of 6-trichlorobenzoic acid is characterized in that:
In the step 3) 2,4, the step of 6-trichlorobenzoic acid crude product refining is:
In reactor, add entry and step 2) make 2,4,6-trichlorobenzoic acid crude product, interpolation concentration is 40% sodium hydroxide, the pH value is adjusted to 10～12, the water that is added, sodium hydroxide and 2,4, the weight ratio of 6-trichlorobenzoic acid crude product is: 3～4:0.45～0.55:1; Adding weight again is 2,4, the gac of 6-trichlorobenzoic acid crude product 1～5%, and 80～100 ℃ kept 1～2 hour, and heat filtering is removed gac; Adjust the temperature to 50～65 ℃ after the filtration, the pH value be adjusted to 1, be cooled to room temperature, filter 2,4,6-trichlorobenzoic acid solid is also dry.
One kind as claimed in claim 12,4, the preparation method of 6-trichlorobenzoic acid is characterized in that:
The crystalline step is in the step 4):
With step 3) obtain 2,4,6-trichlorobenzoic acid solid adds Glacial acetic acid and water, added 2,4, the weight ratio of 6-trichlorobenzoic acid solid, Glacial acetic acid and water is 1:0.9～1.1:0.9～1.1, add gac, heating also kept heat filtering, crystallisation by cooling 0.5～1 hour in 80～90 ℃, filter, obtain 2,4,6-trichlorobenzoic acid crystal.
One kind as claimed in claim 82,4, the preparation method of 6-trichlorobenzoic acid is characterized in that:
The crystalline step is in the step 4):
With step 3) obtain 2,4,6-trichlorobenzoic acid solid adds Glacial acetic acid and water, added 2,4, the weight ratio of 6-trichlorobenzoic acid solid, Glacial acetic acid and water is 1:1:1, adding weight is 2,4, the gac of 6-trichlorobenzoic acid solid 1～5%, heating also kept 0.5～1 hour in 80～90 ℃, heat filtering, crystallisation by cooling filters and obtains 2,4,6-trichlorobenzoic acid crystal.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106928044A (en) * | 2017-03-21 | 2017-07-07 | 上海康鹏科技有限公司 | A kind of preparation method of fluoro phenylacetic acid |
| CN107417509A (en) * | 2017-05-24 | 2017-12-01 | 上海康鹏科技有限公司 | A kind of preparation method of phenylacetic acid compound |
| CN108794320A (en) * | 2017-04-28 | 2018-11-13 | 浙江天宇药业股份有限公司 | A kind of preparation method of 2,4,5- trifluoro benzene acetic acids |
-
2008
- 2008-12-12 CN CNA2008102396525A patent/CN101429117A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106928044A (en) * | 2017-03-21 | 2017-07-07 | 上海康鹏科技有限公司 | A kind of preparation method of fluoro phenylacetic acid |
| CN106928044B (en) * | 2017-03-21 | 2020-08-25 | 上海康鹏科技股份有限公司 | Preparation method of fluorophenylacetic acid |
| CN108794320A (en) * | 2017-04-28 | 2018-11-13 | 浙江天宇药业股份有限公司 | A kind of preparation method of 2,4,5- trifluoro benzene acetic acids |
| CN108794320B (en) * | 2017-04-28 | 2020-04-14 | 浙江天宇药业股份有限公司 | Preparation method of 2,4, 5-trifluorophenylacetic acid |
| CN107417509A (en) * | 2017-05-24 | 2017-12-01 | 上海康鹏科技有限公司 | A kind of preparation method of phenylacetic acid compound |
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