CN104292113A - Preparation method of 3-chloro-4-fluoroaniline - Google Patents
Preparation method of 3-chloro-4-fluoroaniline Download PDFInfo
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- CN104292113A CN104292113A CN201410076299.9A CN201410076299A CN104292113A CN 104292113 A CN104292113 A CN 104292113A CN 201410076299 A CN201410076299 A CN 201410076299A CN 104292113 A CN104292113 A CN 104292113A
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Abstract
The invention discloses a preparation method of 3-chloro-4-fluoroaniline, and belongs to the technical field of organic chemical industry. The preparation method comprises the following steps of weighing 3-chloro-4-fluoronitrobenzene and 1% Pt/C catalyst and reacting for 1-10 hours at a temperature of 50-100 DEG C and in a hydrogen atmosphere of 0.1-5 MPa, wherein a mass ratio of 3-chloro-4-fluoronitrobenzene to 1% Pt/C catalyst is (200-400):1. The preparation method takes 3-chloro-4-fluoronitrobenzene as a raw material and prepares 3-chloro-4-fluoroaniline by a hydrogenation substitution reaction under catalysis of 1% Pt/C catalyst, has high reaction conversion rate, high yield and high selectivity, adopts no organic solvent, is simple and reasonable in process, and is suitable for large-scale production. The purity of 3-chloro-4-fluoroaniline prepared by the method can reach over 99.5%; and the yield reaches over 94%.
Description
Technical field
The present invention is specifically related to the preparation method of the chloro-4-fluoroaniline of a kind of 3-, belongs to field of chemical technology.
Background technology
3-chloro-4-fluoroaniline (FCA) is the main synthesis material intermediate of newly developed novel, efficient, broad spectrum antibiotic-Norxin, Zanocin, Ciprofloxacin, chlorine Norxin etc. in recent years, or the important source material of Fluoric Herbicides, sterilant, is widely used in the fields such as medicine, agricultural chemicals, dyestuff.Along with the rise in field and the universal of medicine, the demand of the chloro-4-fluoroaniline of 3-is increased day by day.Therefore, its synthetic method is subject to the common concern of people.
The synthetic method of 3-chloro-4-fluoroaniline is multiple, wherein most importantly adopts 3-chloro-4-fluoronitrobenzene to prepare the chloro-4-fluoroaniline of 3-through reduction reaction.Under electrolyte solution exists situation, using metallic iron as reductive agent by NO
2be reduced to NH
2.Reaction comprises and add 3-chloro-4-fluorine nitro, reduced iron powder, second alcohol and water in reactor, be heated to 60 DEG C, hydrochloric acid is added wherein again after starting stirring, temperature is made to remain on 80 ~ 90 DEG C, after reacting completely, reaction solution is cooled, adopt organic solvent extraction, slough solvent after drying, filtration, finally distillation obtains 3-chloro-4-fluoroaniline white crystal.This reaction adopts iron powder catalytic reduction, although technique is more ripe, reaction can produce a large amount of acid mist and the iron mud containing phenyl ring amine, seriously polluted.
At present, adopt shortening legal system also comparatively common for halo aniline, but solvent such as fatty alcohol, aromatic hydrocarbons, the tetrahydrofuran (THF)s etc. of adopting participate in reaction more, need distillation or rectifying separation product, operate comparatively loaded down with trivial details after reaction terminates.Such as adopt raney ni catalysis hydrogenation reaction, need first in METHANOL MEDIUM, to pass into H
2reduction displacement, this temperature of reaction is lower, and by product is few, and aftertreatment is simple, effectively can eliminate three-waste pollution, but needs in reaction to use solvent, and solvent recuperation increases certain cost.
Summary of the invention
The object of this invention is to provide the preparation method of the chloro-4-fluoroaniline of a kind of 3-.
In order to realize above object, the technical solution adopted in the present invention is:
A preparation method for the chloro-4-fluoroaniline of 3-, comprises the following steps: get the chloro-4-fluoronitrobenzene of 3-and 1%Pt/C catalyzer, reacts 1 ~ 10 hour at 50 ~ 100 DEG C, in 0.1 ~ 5MPa atmosphere of hydrogen.
Before described reaction is carried out, carry out gas displacement with rare gas element, hydrogen successively, finally make hydrogen pressurize 0.1 ~ 5MPa.Rare gas element can adopt nitrogen, helium etc.
After described reaction terminates, filtered while hot obtains crude product, and namely crude product distillation or rectifying obtain sterling.The concrete steps of rectifying are: under normal pressure, crude product temperature is increased to 100 DEG C, distill out front component; Open vacuum gradually again, collect cut along with intensification and detect, collect 3-chloro-4-fluoroaniline content in cut and be greater than 99.5%, as sterling.
In described reaction, the mass ratio of the chloro-4-fluoronitrobenzene of 3-and 1%Pt/C catalyzer is (200 ~ 400): 1.Wherein, 1%Pt/C catalyzer is commercial goods.
Beneficial effect of the present invention:
The present invention is with the chloro-4-fluoronitrobenzene of 3-for raw material, and adopt the substitution reaction of 1%Pt/C shortening to prepare the chloro-4-fluoroaniline of 3-, reaction conversion ratio, yield and selectivity are high, do not adopt any organic solvent, and technique advantages of simple, is suitable for large-scale industrial production.The 3-chloro-4-fluoroaniline purity adopting the inventive method to prepare reaches more than 99.5%, and yield reaches more than 94%.
Embodiment
Following embodiment is only described in further detail the present invention, but does not form any limitation of the invention.
Embodiment 1
The preparation method of the chloro-4-fluoroaniline of 3-in the present embodiment, comprise the following steps: by chloro-for 3-4-fluoronitrobenzene 600g, 1%Pt/C(is purchased from Kangna Novel Material (Hangzhou) Co., Ltd.) 2g joins in reactor, gas reactor is replaced three times with high pure nitrogen, use hydrogen exchange gas reactor afterwards three times, passing into hydrogen keeps pressure at 0.5MPa, be warming up to 60 DEG C, open and stir, react 8 hours, after reaction terminates, filtered while hot obtains crude product, crude product is carried out rectifying, first at ambient pressure temperature is increased to 100 DEG C, distill out front component, open vacuum gradually again, collect cut along with intensification and detect, obtain the 3-chloro-4-fluoroaniline 467.5g that purity is 99.5%, yield 94%.
Embodiment 2
The preparation method of the chloro-4-fluoroaniline of 3-in the present embodiment, comprise the following steps: by chloro-for 3-4-fluoronitrobenzene 60kg, 1%Pt/C(is purchased from Kangna Novel Material (Hangzhou) Co., Ltd.) 200g joins in reactor, gas reactor is replaced three times with high pure nitrogen, use hydrogen exchange gas reactor afterwards three times, passing into hydrogen keeps pressure at 0.8MPa, be warming up to 80 DEG C, open and stir, react 5 hours, after reaction terminates, filtered while hot obtains crude product, crude product is carried out rectifying, first at ambient pressure temperature is increased to 100 DEG C, distill out front component, open vacuum gradually again, collect cut along with intensification and detect, obtain the 3-chloro-4-fluoroaniline 47.8kg that purity is 99.6%, yield 96%.
Embodiment 3
The preparation method of the chloro-4-fluoroaniline of 3-in the present embodiment, comprise the following steps: by chloro-for 3-4-fluoronitrobenzene 60kg, 1%Pt/C(is purchased from Kangna Novel Material (Hangzhou) Co., Ltd.) 150g joins in reactor, gas reactor is replaced three times with high pure nitrogen, use hydrogen exchange gas reactor afterwards three times, passing into hydrogen keeps pressure at 5.0MPa, be warming up to 50 DEG C, open and stir, react 10 hours, after reaction terminates, filtered while hot obtains crude product, crude product is carried out rectifying, first at ambient pressure temperature is increased to 100 DEG C, distill out front component, open vacuum gradually again, collect cut along with intensification and detect, obtain the chloro-4-fluoroaniline of 3-that purity is 99.7%, yield 94%.
Embodiment 4
The preparation method of the chloro-4-fluoroaniline of 3-in the present embodiment, comprise the following steps: by chloro-for 3-4-fluoronitrobenzene 60kg, 1%Pt/C(is purchased from Kangna Novel Material (Hangzhou) Co., Ltd.) 300g joins in reactor, gas reactor is replaced three times with high pure nitrogen, use hydrogen exchange gas reactor afterwards three times, passing into hydrogen keeps pressure at 0.1MPa, be warming up to 100 DEG C, open and stir, react 1 hour, after reaction terminates, filtered while hot obtains crude product, crude product is carried out rectifying, first at ambient pressure temperature is increased to 100 DEG C, distill out front component, open vacuum gradually again, collect cut along with intensification and detect, obtain the chloro-4-fluoroaniline of 3-that purity is 99.5%, yield 95%.
Claims (5)
1. a preparation method for the chloro-4-fluoroaniline of 3-, is characterized in that: comprise the following steps: get the chloro-4-fluoronitrobenzene of 3-and 1%Pt/C catalyzer, reacts 1 ~ 10 hour at 50 ~ 100 DEG C, in 0.1 ~ 5MPa atmosphere of hydrogen.
2. the preparation method of the chloro-4-fluoroaniline of 3-according to claim 1, is characterized in that: before described reaction is carried out, and carries out gas displacement successively, finally make hydrogen pressurize 0.1 ~ 5MPa with rare gas element, hydrogen.
3. the preparation method of the chloro-4-fluoroaniline of 3-according to claim 1, is characterized in that: after described reaction terminates, filtered while hot obtains crude product, and namely crude product distillation or rectifying obtain sterling.
4. the preparation method of the chloro-4-fluoroaniline of 3-according to claim 3, is characterized in that: the step of described rectifying is: under normal pressure, crude product temperature is increased to 100 DEG C, distills out front component; Open vacuum gradually again, collect cut along with intensification and detect, collect 3-chloro-4-fluoroaniline content in cut and be greater than 99.5%.
5. the preparation method of the chloro-4-fluoroaniline of 3-according to claim 1, is characterized in that: in described reaction, the mass ratio of the chloro-4-fluoronitrobenzene of 3-and 1%Pt/C catalyzer is (200 ~ 400): 1.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105418439A (en) * | 2015-11-17 | 2016-03-23 | 山东沾化天九化工有限公司 | Method and device for producing 3-chlorine-4-fluoroaniline |
| CN105859565A (en) * | 2016-05-05 | 2016-08-17 | 成都中恒华铁科技有限公司 | Synthetic method of norfloxacin drug intermediate 3-chloro-4-fluoroaniline |
| CN106349084A (en) * | 2016-08-26 | 2017-01-25 | 安徽省虹升生物股份有限公司 | Preparation method of 4-fluoro-3-chloroaniline |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103285856A (en) * | 2013-06-09 | 2013-09-11 | 南通市华峰化工有限责任公司 | Anti-dehalogenation ruthenium-based catalyst for preparing halogenated phenylamine and preparation method thereof |
| CN103333075A (en) * | 2013-07-11 | 2013-10-02 | 江苏扬农化工集团有限公司 | Production method of 2,5-dichloroaniline |
-
2014
- 2014-03-04 CN CN201410076299.9A patent/CN104292113A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103285856A (en) * | 2013-06-09 | 2013-09-11 | 南通市华峰化工有限责任公司 | Anti-dehalogenation ruthenium-based catalyst for preparing halogenated phenylamine and preparation method thereof |
| CN103333075A (en) * | 2013-07-11 | 2013-10-02 | 江苏扬农化工集团有限公司 | Production method of 2,5-dichloroaniline |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105418439A (en) * | 2015-11-17 | 2016-03-23 | 山东沾化天九化工有限公司 | Method and device for producing 3-chlorine-4-fluoroaniline |
| CN105859565A (en) * | 2016-05-05 | 2016-08-17 | 成都中恒华铁科技有限公司 | Synthetic method of norfloxacin drug intermediate 3-chloro-4-fluoroaniline |
| CN106349084A (en) * | 2016-08-26 | 2017-01-25 | 安徽省虹升生物股份有限公司 | Preparation method of 4-fluoro-3-chloroaniline |
| CN106349084B (en) * | 2016-08-26 | 2018-08-07 | 安徽省虹升生物股份有限公司 | A kind of preparation method of the fluoro- 3- chloroanilines of 4- |
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