CN101362699A - Method for synthesizing 2,4-dichloroaniline - Google Patents
Method for synthesizing 2,4-dichloroaniline Download PDFInfo
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- CN101362699A CN101362699A CNA2008101616087A CN200810161608A CN101362699A CN 101362699 A CN101362699 A CN 101362699A CN A2008101616087 A CNA2008101616087 A CN A2008101616087A CN 200810161608 A CN200810161608 A CN 200810161608A CN 101362699 A CN101362699 A CN 101362699A
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Abstract
The invention discloses a method for synthesizing 2, 4-dichloroaniline, which adopts parachloronitrobenzene as raw material and comprises the steps as follows: firstly, nitro-benzene is reduced into the corresponding hydroxylamine in the alcohol-water solution of ammonium chloride; secondly, chloro of benzene ring and reduction of hydroxylamine are carried out simultaneously in the hydrochloric acid solution; and thirdly, the pH value is adjusted until the solids are precipitated, and 2,4-dichloroaniline can be obtained after recrystallization by using the alcohol-water solution. The hydrochloric acid in this invention is adopted not only as a source of hydrogen for reduction reaction, but also as a chlorination agent for chlorination reaction, the reduction reaction and the chlorination reaction can be finished at the same time, the invention has the advantages of short process route, no high requirement for devices, simple operation, and high yield of 2,4-dichloroaniline, no usage of expensive catalysts, low raw material and production cost and being suitable for industrial production.
Description
Technical field
The present invention relates to a kind of Synthetic 2, the method for 4-dichlorphenamide bulk powder.
Background technology
2,4 dichloro aniline is important dye well medicine intermediate, is widely used in fine chemistry industry industries such as agricultural chemicals, medicine, dyestuff, sensitive materials.This product of China mainly relies on import at present.The major cause that causes this present situation is that the 2,4 dichloro aniline production process route of China is longer, the cost height, and to compare competitive power low with external product.By oil of mirbane is raw material, and the traditional method of preparation 2,4 dichloro aniline must be through four-step reactions such as reduction, acidylate, chlorination and deacylated tRNA bases.Except that having a chlorine, many chlorine by product, also there is the positional isomers of 2,4 dichloro aniline in the product of this technology, separates relatively difficulty and influence quality product.Simultaneously, this technology uses chlorine to be chlorizating agent, considers the rate of utilization of chlorine lower (chlorine that half is arranged is not utilized and has generated hydrogenchloride) from atom utilization.In addition, chlorine is nonhomogeneous system as the reaction system of chlorizating agent, generally needs excessive chlorine can reach certain transformation efficiency, thereby increases consumption of raw materials and aftertreatment load.The 2,4 dichloro aniline of bibliographical information improvement synthetic method mainly contains at present:
1. (Zhang Sigui edits Fine Organic Chemical product technical manual Beijing to the Acetanilide raw material route: Science Press, 1991), with the Acetanilide is raw material, uses the clorox chlorination in dilute acetic acid solution, and the intermediate product of generation is again through alcoholysis, acidolysis and obtain product.The characteristics of this process are to adopt hypochlorous acid to substitute chlorine as chlorizating agent.
Using hypochlorous acid in the Acetanilide raw material route method instead is chlorizating agent, and atom utilizes chlorine efficient to improve, and is homogeneous reaction, and reaction is control easily.But this operational path requires to be reflected in the acetum to carry out, and reclaims the acetic acid loss in the acetic acid process, the energy and devices consume, and artificial etc. production cost is obviously improved.
2. Meta Dichlorobenzene is that (Cai Chun 2 for raw material route, the 33 volume first phases in 1996 of synthetic dyestuff industry of 4-dichlorphenamide bulk powder), this technology is raw material with the Meta Dichlorobenzene, after nitric acid, vitriolic mixed acid solution are nitrated, with iron powder in acid medium, stirring and refluxing obtains 2,4 dichloro aniline, and product yield can reach more than 90% under the optimal conditions.But the stock yard dichlorobenzene of this method is generally obtained through chlorinated with chlorine by benzene or Benzene Chloride, and what mainly obtain is contraposition and 0-dichlorobenzene, obtain a spot of Meta Dichlorobenzene after must separating, so not only cost of material is higher and be not easy to obtain.In addition, obtain, the conventional production methods of 2,4 dichloro aniline is not had in essence improvement because the stock yard dichlorobenzene of this method still must be chlorizating agent with chlorine.
3. (JP 3209347 (1991) for the parachloronitrobenzene raw material route, the nineties, Japanese Patent proposed a kind of method, main process is: be raw material with the parachloronitrobenzene, in acidproof autoclave, add methylethylketone, Palladous chloride, triphenyl phosphorus, hydrochloric acid etc., and the feeding CO (carbon monoxide converter) gas, at 7MPa, temperature of reaction be react under 130 ℃ 2, the 4-dichlorphenamide bulk powder, productive rate 84%.The characteristics of this method maximum are to be set out by raw material parachloronitrobenzene cheap and easy to get, and nitroreduction and phenyl ring chlorination are carried out simultaneously, and use hydrochloric acid to be chlorizating agent.
The parachloronitrobenzene raw material route method of Japanese Patent, shortened operational path effectively, use hydrochloric acid to be chlorizating agent simultaneously, not only atom utilizes chlorine efficient to improve, and hydrochloric acid is promptly as the hydrogen source of nitroreduction, also be the chlorizating agent of chlorination reaction, make two-step reaction can realize in one pot reaction that productive rate is higher.But this method needs to react under pressure and the comparatively high temps, also to use number of chemical product and expensive palladium chloride catalysts such as methylethylketone, triphenyl phosphorus, carbon monoxide, relate to the processing and the recovery of number of chemical product, the cost in the suitability for industrialized production is wayward.
Summary of the invention
The purpose of this invention is to provide that a kind of operational path is short, simple to operate, facility investment is few, the Synthetic 2 that cost is low, the method for 4-dichlorphenamide bulk powder.
Synthetic 2 of the present invention, the method for 4-dichlorphenamide bulk powder is to be raw material with the parachloronitrobenzene, realizes through following reaction process:
The present invention has following two kinds of technical solutions:
Scheme 1:
Synthetic 2, the method for 4-dichlorphenamide bulk powder may further comprise the steps, and following concentration is mass concentration:
1) methyl alcohol of concentration 25～35% parachloronitrobenzenes or the aqueous ammonium chloride solution of ethanolic soln and concentration 5～10% are added in the reactor, the weight ratio of parachloronitrobenzene and ammonium chloride is 10:1, heated and stirred under the nitrogen protection, when reaching 75-80 ℃, temperature adds reductive agent, the weight ratio of parachloronitrobenzene and reductive agent is 1:1～3, the adding speed of control reductive agent maintains 75-80 ℃ to keep temperature of reaction, and reductive agent finishes afterreaction liquid and is back to water white transparency;
2) cooling is stirred in nitrogen protection down, when being lower than 60 ℃, temperature slowly adds concentrated hydrochloric acid, and keep keeping temperature of reaction at 55-60 ℃ in the concentrated hydrochloric acid adition process, the weight ratio of parachloronitrobenzene and concentrated hydrochloric acid is 1:15～20, concentrated hydrochloric acid adds back 60 ℃ and reacted 1～3 hour down;
3) above-mentioned reaction solution is cooled to room temperature, filters and discards filter residue, regulates filtrate pH value and separate out to solid in ice bath, and the gained solid is recrystallization in the alcohol solution of concentration 40～60%, gets the 2,4 dichloro aniline white needle-like crystals.
Above-mentioned alcohol solution is ethanol or methanol in water.
Scheme 2
Synthetic 2, the method for 4-dichlorphenamide bulk powder may further comprise the steps, and following concentration is mass concentration:
1) methyl alcohol of concentration 25～35% parachloronitrobenzenes or the aqueous ammonium chloride solution of ethanolic soln and concentration 5～10% are added in the reactor, the weight ratio of parachloronitrobenzene and ammonium chloride is 10:1, heated and stirred under the nitrogen protection, when reaching 75-80 ℃, temperature adds reductive agent, the weight ratio of parachloronitrobenzene and reductive agent is 1:1～3, the adding speed of control reductive agent is to keep temperature of reaction at 75-80 ℃, and reductive agent finishes afterreaction liquid and is back to water white transparency;
2) take advantage of the above-mentioned reaction solution of heat filtering, use the hot wash filter cake, after filtrate and washings merge, add trash ice and leave standstill, cool off and separate out solid, filter, use the petroleum ether filter cake, get white plates azanol crystal;
3) azanol is mixed with methyl alcohol or the ethanolic soln of concentration 15-25%, under nitrogen protection is stirred, slowly be added drop-wise in the reactor that fills concentrated hydrochloric acid, the weight ratio of azanol and concentrated hydrochloric acid is 1:8～10, keep temperature of reaction in the dropping process at 55-60 ℃, add afterreaction liquid backflow 30-60 minute;
4) reaction solution is cooled to the room temperature after-filtration, regulates filtrate pH value and separates out to solid, and recrystallization gets white needles 2,4 dichloro aniline crystal.
In above-mentioned two kinds of schemes, said reductive agent can adopt zinc powder, iron powder or tin protochloride.The concentration of the concentrated hydrochloric acid that adopts is 36-37%.
2,4 dichloro aniline synthetic method of the present invention is will become corresponding azanol to the benzene nitroreduction earlier in aqueous ammonium chloride solution, carries out the reduction of the chloro and the azanol of phenyl ring then in hydrochloric acid soln simultaneously.Wherein hydrochloric acid is azanol reductive hydrogen source, also is homogeneous phase chlorating chlorine source.Because in this reaction system, chlorion reacts as nucleophilic reagent and phenyl ring, the ortho position of a chlorine negative ion attack azanol base, thereby the selectivity height of reaction, byproduct of reaction is few, good product quality.And the first step reduction reaction product azanol can be without separating phenyl ring chlorination and the azanol reduction that directly carry out next step simultaneously, effective simplification technological process.
Beneficial effect of the present invention is:
1) the main raw material p-Chlorobenzoic acid amide of Shi Yonging is cheap and easy to get, and chlorizating agent is an aqueous hydrochloric acid, atom utilization height not only, and be the homogeneous phase chlorination reaction, and operation is easy and be easy to control.
2) this method does not need complex apparatus, and technology is simple, does not use special catalyst, and aftertreatment is simple, is comparatively clean production technique.
3) the first step reduzate azanol of nitro can obtain 2,4 dichloro aniline without separating the azanol reduction of directly carrying out next step simultaneously and phenyl ring chlorination, this good reaction selectivity, and yield is higher.Can reduce raw materials consumption and production cost effectively.
With existing preparation 2,4-dichlorphenamide bulk powder method compares, and especially (JP3209347 (1991) compares, and method productive rate of the present invention is near Japanese Patent with Japanese Patent, but need not use special chemical auxiliary material and expensive palladium catalyst, reaction conditions gentleness (need not pressurize and high temperature), last handling process is simpler, on equipment material, except that requirement for anticorrosion, do not have other particular requirement, thereby effectively reduce raw materials cost and production cost, and higher production security is arranged.
Embodiment
Embodiment 1:
Add 20ml ethanol and 6.3g parachloronitrobenzene in the 50ml three-necked bottle, add the aqueous ammonium chloride solution of 12.6ml5% after the stirring and dissolving.Stirring heating under the nitrogen protection adds the 6.5g zinc powder in batches, adds in the zinc powder process 75 ℃ of controlled temperature, keeps this temperature behind reinforced the finishing and is stirred to the reaction solution water white transparency.
Above-mentioned reaction solution is cooled to after temperature is lower than 60 ℃, slowly is added dropwise to 95 gram concentrated hydrochloric acids under nitrogen protection, and controlled temperature is at 55-60 ℃ and stir therebetween.After dripping concentrated hydrochloric acid, 60 ℃ were reacted 1 hour.Be cooled to room temperature, filtration, discard yellow filter residue, filtrate is neutralized to pH=7 with ammoniacal liquor under condition of ice bath, separate out solid, with getting 2,4 dichloro aniline crystal 4 .8g, productive rate 74% behind the 50% aqueous ethanolic solution recrystallization.
Embodiment 2:
Add 20ml ethanol and 6.3g parachloronitrobenzene in the 50ml three-necked bottle, add the aqueous ammonium chloride solution of 12.6ml5% after the stirring and dissolving.Under the stirring heating under the nitrogen protection, 80 ℃ of controlled temperature, add the 10g zinc powder in batches, continue to keep this temperature after adding, be stirred to the reaction solution water white transparency.
Take advantage of heat filtering, with an amount of hot wash filter cake, the adding trash ice leaves standstill to cool off and separates out crystal behind merging filtrate and the washings.Filter the gained crystal after with petroleum ether 4.5g to chlorobenzene azanol crystal, azanol yield 78%.
4.5g the azanol crystal is dissolved in the 25ml ethanol, under nitrogen protection and the stirring, drips the azanol ethanolic soln in the three-necked bottle that fills 36 gram concentrated hydrochloric acids with constant pressure funnel, 60 ℃ of this process control temps react 30 minutes stopped reaction under 60 ℃ after reinforced the finishing.Be cooled to the room temperature after-filtration, filtrate is neutralized to pH=7 with ammoniacal liquor, separates out solid.Aqueous ethanolic solution recrystallization with 50% gets 2,4 dichloro aniline white needle-like crystals 4.1g, 2,4 dichloro aniline yield 63% (in the raw material parachloronitrobenzene).
Embodiment 3:
As the Zn powder in the reductive agent alternate embodiment 1, the tin protochloride consumption is 14g with tin protochloride, and the charging capacity of all the other reagent is all identical with embodiment 1, press the same reaction conditions of embodiment 1 and method of operation in operation final 2,4-dichlorphenamide bulk powder 5.2g, 2,4 dichloro aniline productive rate 80%.
Embodiment 4:
As the Zn powder in the reductive agent alternate embodiment 1, the reduced iron powder consumption is 16g with reduced iron powder, and all the other reagent dosages are all identical with embodiment 1, press identical reaction conditions of embodiment 1 and method of operation in operation final 2,4-dichlorphenamide bulk powder 4.0g, 2,4 dichloro aniline productive rate 61%.
Embodiment 5:
The ethanol of the dissolving parachloronitrobenzene among the embodiment 1 substitutes with methyl alcohol, and the consumption of all the other reagent and operation are all identical with embodiment 1, final 2,4 dichloro aniline 4.8g, the 2,4 dichloro aniline productive rate 74% of getting.
Embodiment 6:
The ethanol of the dissolving parachloronitrobenzene among the embodiment 1 substitutes with methyl alcohol, and the reductive agent zinc powder substitutes with tin protochloride, tin protochloride 12g, the consumption of all the other reagent and operation are all identical with embodiment 1, the final 2,4 dichloro aniline 5.0g that gets, 2,4 dichloro aniline productive rate 77%.
Embodiment 7:
With the reductive agent zinc powder in the tin protochloride alternate embodiment 2, tin protochloride consumption 12g, the consumption of all the other reagent and operation are all identical with embodiment 2, final must be to chlorobenzene azanol crystal 4 .4g, azanol productive rate 77%.
Claims (5)
1. Synthetic 2, the method for 4-dichlorphenamide bulk powder is characterized in that may further comprise the steps, and following concentration is mass concentration:
1) methyl alcohol of concentration 25～35% parachloronitrobenzenes or the aqueous ammonium chloride solution of ethanolic soln and concentration 5～10% are added in the reactor, the weight ratio of parachloronitrobenzene and ammonium chloride is 10:1, heated and stirred under the nitrogen protection, when reaching 75-80 ℃, temperature adds reductive agent, the weight ratio of parachloronitrobenzene and reductive agent is 1:1～3, the adding speed of control reductive agent maintains 75-80 ℃ to keep temperature of reaction, and reductive agent finishes afterreaction liquid and is back to water white transparency;
2) cooling is stirred in nitrogen protection down, when being lower than 60 ℃, temperature slowly adds concentrated hydrochloric acid, and keep keeping temperature of reaction at 55-60 ℃ in the concentrated hydrochloric acid adition process, the weight ratio of parachloronitrobenzene and concentrated hydrochloric acid is 1:15～20, concentrated hydrochloric acid adds back 60 ℃ and reacted 1～3 hour down;
3) above-mentioned reaction solution is cooled to room temperature, filters and discards filter residue, regulates filtrate pH value and separate out to solid in ice bath, and the gained solid is recrystallization in the alcohol solution of concentration 40～60%, gets the 2,4 dichloro aniline white needle-like crystals.
2. Synthetic 2 according to claim 1, the method for 4-dichlorphenamide bulk powder is characterized in that said reductive agent is zinc powder, iron powder or tin protochloride.
3. Synthetic 2 according to claim 1, the method for 4-dichlorphenamide bulk powder is characterized in that said alcohol solution is ethanol or methanol in water.
4. Synthetic 2, the method for 4-dichlorphenamide bulk powder is characterized in that may further comprise the steps, and following concentration is mass concentration:
1) methyl alcohol of concentration 25～35% parachloronitrobenzenes or the aqueous ammonium chloride solution of ethanolic soln and concentration 5～10% are added in the reactor, the weight ratio of parachloronitrobenzene and ammonium chloride is 10:1, heated and stirred under the nitrogen protection, when reaching 75-80 ℃, temperature adds reductive agent, the weight ratio of parachloronitrobenzene and reductive agent is 1:1～3, the adding speed of control reductive agent is to keep temperature of reaction at 75-80 ℃, and reductive agent finishes afterreaction liquid and is back to water white transparency;
2) take advantage of the above-mentioned reaction solution of heat filtering, use the hot wash filter cake, after filtrate and washings merge, add trash ice and leave standstill, cool off and separate out solid, filter, use the petroleum ether filter cake, get white plates azanol crystal;
3) azanol is mixed with methyl alcohol or the ethanolic soln of concentration 15-25%, under nitrogen protection is stirred, slowly be added drop-wise in the reactor that fills concentrated hydrochloric acid, the weight ratio of azanol and concentrated hydrochloric acid is 1:8～10, keep temperature of reaction in the dropping process at 55-60 ℃, add afterreaction liquid backflow 30-60 minute;
4) reaction solution is cooled to the room temperature after-filtration, regulates filtrate pH value and separates out to solid, and recrystallization gets white needles 2,4 dichloro aniline crystal.
5. Synthetic 2 according to claim 1, the method for 4-dichlorphenamide bulk powder is characterized in that said reductive agent is zinc powder, iron powder or tin protochloride.
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| CN2008101616087A CN101362699B (en) | 2008-09-16 | 2008-09-16 | Method for synthesizing 2,4-dichloroaniline |
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| CN2008101616087A CN101362699B (en) | 2008-09-16 | 2008-09-16 | Method for synthesizing 2,4-dichloroaniline |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102617401A (en) * | 2012-03-08 | 2012-08-01 | 象山志华新材料有限公司 | Synthesis method for co-producing p-chloroaniline and p-chlorophenol isocyanate |
| CN102863342A (en) * | 2012-10-17 | 2013-01-09 | 湖北美天生物科技有限公司 | Preparation method of high-purity 2, 6-dichloro-4-trifluoromethyl aniline |
| CN112011194A (en) * | 2019-05-30 | 2020-12-01 | 浙江闰土研究院有限公司 | Disperse dye composition, preparation method thereof and treatment method of dye intermediate of disperse dye composition |
| CN112358404A (en) * | 2020-11-09 | 2021-02-12 | 扬州市普林斯医药科技有限公司 | Preparation method of 2-chloro-6-methylaniline |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3209347B2 (en) * | 1991-07-08 | 2001-09-17 | コーア株式会社 | Magnetic effect element, method of manufacturing the same, and magnetic therapy device using the magnetic effect element |
-
2008
- 2008-09-16 CN CN2008101616087A patent/CN101362699B/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102617401A (en) * | 2012-03-08 | 2012-08-01 | 象山志华新材料有限公司 | Synthesis method for co-producing p-chloroaniline and p-chlorophenol isocyanate |
| CN102863342A (en) * | 2012-10-17 | 2013-01-09 | 湖北美天生物科技有限公司 | Preparation method of high-purity 2, 6-dichloro-4-trifluoromethyl aniline |
| CN112011194A (en) * | 2019-05-30 | 2020-12-01 | 浙江闰土研究院有限公司 | Disperse dye composition, preparation method thereof and treatment method of dye intermediate of disperse dye composition |
| CN112358404A (en) * | 2020-11-09 | 2021-02-12 | 扬州市普林斯医药科技有限公司 | Preparation method of 2-chloro-6-methylaniline |
| CN112358404B (en) * | 2020-11-09 | 2023-01-20 | 扬州市普林斯医药科技有限公司 | Preparation method of 2-chloro-6-methylaniline |
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