CN108947849A - A kind of method of solvent-free catalytic hydrogenation production 2,4 difluorobenzene amine - Google Patents
A kind of method of solvent-free catalytic hydrogenation production 2,4 difluorobenzene amine Download PDFInfo
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- CN108947849A CN108947849A CN201810941028.3A CN201810941028A CN108947849A CN 108947849 A CN108947849 A CN 108947849A CN 201810941028 A CN201810941028 A CN 201810941028A CN 108947849 A CN108947849 A CN 108947849A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
- C07C209/365—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst by reduction with preservation of halogen-atoms in compounds containing nitro groups and halogen atoms bound to the same carbon skeleton
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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Abstract
The present invention provides a kind of solvent-free catalytic hydrogenation productions 2, the method of 4- difluoroaniline, with 2, 4- difluoro nitrobenzene is raw material, under condition of no solvent, the catalytic hydrogenation preparation 2 in autoclave under the conditions of adding catalyst and phosphate, 4- difluoroaniline, the present invention is using solvent-free plus hydrogen method, solvent compared to the past adds hydrogen, greatly increase the efficiency of reaction, utilization rate of equipment and installations significantly improves, recycling design bring energy consumption and cost of equipment can be effectively avoided simultaneously, belong to the environmentally friendly technique of green non-pollution, effectively avoid generating a large amount of waste water, waste residue.The present invention uses this noble metal catalyst of Pt/C, has preparation simple, catalyst itself can be recycled in the reaction, and metal can recycle, to further decrease production cost, dehydrogenation inhibitor is acted not only as using phosphate, and reaction conversion ratio can be improved.
Description
Technical field
The invention belongs to technical field of catalytic hydrogenation, and in particular to a kind of solvent-free catalytic hydrogenation production 2,4- difluorobenzene
The method of amine.
Background technique
2,4- difluoroanilines are the intermediates of organic synthesis, are pharmaceutically used for the conjunction of diflunisal and A-6096
At.Difunisal is carboxylic acids non-steroidal anti-inflammatory drug, and the acetyl group of aspirin is not contained in salicylic new derivative structure
And contain difluorophenyl, thus antiplatelet Small side effects, and gastrointestinal reaction is slight, action time can maintain 8-12h, be
Most promising kind in Salicylates.Mostly used greatly on medical industry at present m-phenylene diamine (MPD) through diazotising, displacement,
Nitrification is restored and is obtained.But this method synthesis process is more complicated, final reaction yield result is simultaneously unstable.2,4- bis-
Fluoroaniline is reduced as diflunisal pharmaceutical intermediate, synthetic method superiority and inferiority for improving pharmaceutical synthesis product quality
By-products content has Important Economic meaning.
Wang Qiuling (Wang Qiuling pays vertical people .2, synthesis [J] the Organic fluoride industry of 4- difluoroaniline, 1991,02:25-29.)
With 2,4- difluoro nitrobenzene for raw material, using iron powder as reducing agent in aqueous ammonium chloride solution, back flow reaction is carried out, synthesizes 2,4- bis-
Fluoroaniline, although reaction is relatively simple, the reaction yield of this synthetic method is only 87 .8%, and can be generated a large amount of useless
Therefore water and iron cement solid waste to improve reaction yield, reduce the three wastes and generate, it would be highly desirable to propose a kind of new synthetic method.
Summary of the invention
To solve the above-mentioned problems, the present invention provides a kind of side of solvent-free catalytic hydrogenation production 2,4- difluoroaniline
Method, it is this method simple process, high income, at low cost, environmentally protective.
The present invention is achieved by the following technical solutions:
A kind of method of solvent-free catalytic hydrogenation production 2,4- difluoroaniline, it is solvent-free with 2,4- difluoro nitrobenzene for raw material
Under the conditions of, catalytic hydrogenation prepares 2,4- difluoroaniline in autoclave under the conditions of adding catalyst and phosphate.
Preferably, the catalyst is Pt/C catalyst, and the Pt load capacity of catalyst is 1% or 3%, dosage 2,4- bis-
The 0.5%-1% of fluoronitrobenzene quality.
Preferably, the phosphate be one of sodium hypophosphite, hydrogen phosphite sodium, disodium hydrogen phosphate, sodium phosphate,
Dosage is the 1%-3% of 2,4- difluoro nitrobenzene quality.
Preferably, the condition of catalytic hydrogenation are as follows: pressure 0.5-2.0Mpa, reaction temperature are 30-150 DEG C.
The step of catalytic hydrogenation reaction described above are as follows:
(1) by 2, the 4- difluoro nitrobenzene, catalyst, phosphate is added in autoclave, and nitrogen, hydrogen are respectively replaced three times；
(2) stirring is opened, 30-90 DEG C is warming up to, is passed through hydrogen 0.5-2.0Mpa, start to react, control reaction temperature is 30-
150℃；
(3) in reaction process, the instantaneous velocity of reaction of reaction is measured, is dropped with the interior Hydrogen Vapor Pressure reacted per minute to indicate, instead
Answer speed are as follows: 0.10-0.3Mpa/min；
(4) the reaction used time is 1-4 hours, at the end of reaction, and reaction pressure increases, and reaction temperature reduces, reaction speed zero；
(5) by way of suction filtration, catalyst and reaction solution are separated, reaction solution simply divides water, obtains most after vacuum distillation
Finished product 2,4 difluorobenzene amine.
The conversion ratio of the reaction of product obtained by the above method is 100%, product purity>99.5%, defluorinate<0.2%, product
Yield > 98%.
Beneficial effect
(1) for the present invention using solvent-free plus hydrogen method, the solvent compared to the past adds hydrogen, greatly increases the efficiency of reaction,
Utilization rate of equipment and installations significantly improves, while can effectively avoid recycling design bring energy consumption and cost of equipment.
(2) method that the present invention uses catalytic hydrogenation, belongs to the environmentally friendly technique of green non-pollution, effectively avoids producing
Raw a large amount of waste water, waste residue.
(3) present invention uses this noble metal catalyst of Pt/C, has preparation simple, and catalyst itself in the reaction can be with
It is recycled, and metal can recycle, to further decrease production cost.
(4) present invention uses lower reaction temperature and reaction pressure, and 2,4- difluoroaniline is prepared, and has technique letter
The advantages of list, high income.
(5) present invention acts not only as dehydrogenation inhibitor using phosphate, and reaction conversion ratio can be improved, and reacts
Time is shorter, 1-4 hour can fully reacting, and yield is higher, and defluorinate rate is lower.
Specific embodiment
It elaborates below to the embodiment of the present invention, the present embodiment carries out under the premise of the technical scheme of the present invention
Implement, the detailed implementation method and specific operation process are given, but protection scope of the present invention is not limited to following implementation
Example.
Embodiment 1
(1) by 200g2,4- difluoro nitrobenzene, 1g 1%Pt/C catalyst, 1g sodium hypophosphite is added in autoclave, nitrogen,
Hydrogen is respectively replaced three times.
(2) stirring is opened, 70 DEG C is warming up to, is passed through hydrogen 0.9Mpa, start to react, control reaction temperature is 90 DEG C.
(3) in reaction process, the instantaneous velocity of reaction of reaction is measured, table is come with the Hydrogen Vapor Pressure drop reacted interior per minute
Show, reaction speed are as follows: 0.12Mpa/min.
(4) the reaction used time is 3 hours, at the end of reaction, and reaction pressure increases, and reaction temperature reduces, reaction speed zero.
(5) by way of suction filtration, catalyst and reaction solution are separated, reaction solution simply divides water, after vacuum distillation
To final products 2,4- difluoroaniline, the conversion ratio of reaction is 100%, product purity 99.8%, defluorinate 0.12%, product yield
98.5%。
Embodiment 2
Under the premise of embodiment 1, carry out catalyst applies experiment (i.e. catalyst circulation use):
(1) by 200g2,4- difluoro nitrobenzene adds 0.2g 1%Pt/C catalyst, and 1g sodium hypophosphite is added in autoclave,
Nitrogen, hydrogen are respectively replaced three times.
(2) stirring is opened, 70 DEG C is warming up to, is passed through hydrogen 0.9Mpa, start to react, control reaction temperature is 90 DEG C.
(3) in reaction process, the instantaneous velocity of reaction of reaction is measured, table is come with the Hydrogen Vapor Pressure drop reacted interior per minute
Show, reaction speed are as follows: 0.13Mpa/min.
(4) the reaction used time is 45 minutes 2 hours, at the end of reaction, and reaction pressure increases, and reaction temperature reduces, reaction speed
Degree is zero.
(5) by way of suction filtration, catalyst and reaction solution are separated, reaction solution simply divides water, after vacuum distillation
To final products 2,4- difluoroaniline, the conversion ratio of reaction is 100%, product purity 99.78%, defluorinate 0.11%, product yield
98.6%。
Embodiment 3:
Continuing to apply 10 batches under the premise of embodiment 1, embodiment 2, to obtain result as follows:
Wherein serial number 8 is that the sodium hypophosphite in embodiment 1 is changed to sodium phosphate, and other conditions are constant；
Serial number 9 is that the sodium hypophosphite in embodiment 1 is changed to disodium hydrogen phosphate, and other conditions are constant；
Serial number 10 is that the sodium hypophosphite in embodiment 1 is changed to hydrogen phosphite sodium, and other conditions are constant；
It is 30 DEG C that serial number 11, which is by the control reaction temperature in embodiment 1, and other conditions are constant；
It is 150 DEG C that serial number 12, which is by the control reaction temperature in embodiment 1, and other conditions are constant.
Embodiment 4:
(1) by 200g2,4- difluoro nitrobenzene, 1g 3%Pt/C catalyst, 2g sodium hypophosphite is added in autoclave, nitrogen,
Hydrogen is respectively replaced three times.
(2) stirring is opened, 60 DEG C is warming up to, is passed through hydrogen 1.0Mpa, start to react, control reaction temperature is 95 DEG C.
(3) in reaction process, the instantaneous velocity of reaction of reaction is measured, table is come with the Hydrogen Vapor Pressure drop reacted interior per minute
Show, reaction speed are as follows: 0.22Mpa/min.
(4) the reaction used time is 1 hour 50min, and at the end of reaction, reaction pressure is increased, and reaction temperature reduces, reaction speed
It is zero.
(5) by way of suction filtration, catalyst and reaction solution are separated, reaction solution simply divides water, after vacuum distillation
To final products 2,4- difluoroaniline, the conversion ratio of reaction is 100%, product purity 99.60%, defluorinate 0.21%, product yield
98.21%。
Obviously, various changes and modifications can be made to the invention without departing from essence of the invention by those skilled in the art
Mind and range.In this way, if these modifications and changes of the present invention belongs to the range of the claims in the present invention and its equivalent technologies
Within, then the present invention is also intended to include these modifications and variations.
Claims (5)
1. a kind of method of solvent-free catalytic hydrogenation production 2,4- difluoroaniline, it is characterised in that: with 2,4- difluoro nitrobenzene
For raw material, under condition of no solvent, catalytic hydrogenation prepares 2,4- difluoro in autoclave under the conditions of adding catalyst and phosphate
Aniline.
2. the method according to claim 1, wherein the catalyst is Pt/C catalyst, the Pt of catalyst
Load capacity is 1% or 3%, dosage 2, the 0.5%-1% of 4- difluoro nitrobenzene quality.
3. the method according to claim 1, wherein the phosphate be sodium hypophosphite, hydrogen phosphite sodium,
One of disodium hydrogen phosphate, sodium phosphate, dosage 2, the 1%-3% of 4- difluoro nitrobenzene quality.
4. according to the method described in claim 2, it is characterized in that, the condition of catalytic hydrogenation are as follows: pressure 0.5-2.0Mpa, instead
Answering temperature is 30-150 DEG C.
5. method described in one of -4 according to claim 1, which is characterized in that the step of catalytic hydrogenation reaction are as follows:
(1) by 2, the 4- difluoro nitrobenzene, catalyst, phosphate is added in autoclave, and nitrogen, hydrogen are respectively replaced three times；
(2) stirring is opened, 30-90 DEG C is warming up to, is passed through hydrogen 0.5-2.0Mpa, start to react, control reaction temperature is 30-
150℃；
(3) in reaction process, the instantaneous velocity of reaction of reaction is measured, is dropped with the interior Hydrogen Vapor Pressure reacted per minute to indicate, instead
Answer speed are as follows: 0.10-0.3Mpa/min；
(4) the reaction used time is 1-4 hours, at the end of reaction, and reaction pressure increases, and reaction temperature reduces, reaction speed zero；
(5) by way of suction filtration, catalyst and reaction solution are separated, reaction solution simply divides water, obtains most after vacuum distillation
Finished product 2,4 difluorobenzene amine.
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| CN201810941028.3A CN108947849A (en) | 2018-08-17 | 2018-08-17 | A kind of method of solvent-free catalytic hydrogenation production 2,4 difluorobenzene amine |
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| CN201810941028.3A CN108947849A (en) | 2018-08-17 | 2018-08-17 | A kind of method of solvent-free catalytic hydrogenation production 2,4 difluorobenzene amine |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115650859A (en) * | 2022-10-21 | 2023-01-31 | 利尔化学股份有限公司 | Preparation method of 2,4-difluoroaniline |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0519247A2 (en) * | 1991-06-19 | 1992-12-23 | BASF Aktiengesellschaft | Process for the preparation of halogenated anilines |
| CN101811973A (en) * | 2010-04-23 | 2010-08-25 | 浙江工业大学 | Method for synthesizing halogen aromatic amines by high-selectivity liquid phase hydrogenation under the condition of no solvent |
| CN103242168A (en) * | 2013-04-02 | 2013-08-14 | 淮安嘉诚高新化工股份有限公司 | Dehalogenation inhibitor |
| CN104163764A (en) * | 2014-08-07 | 2014-11-26 | 浙江工业大学 | Method for synthesising halogenated aromatic amine through hydrogenation in solvent-free condition |
-
2018
- 2018-08-17 CN CN201810941028.3A patent/CN108947849A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0519247A2 (en) * | 1991-06-19 | 1992-12-23 | BASF Aktiengesellschaft | Process for the preparation of halogenated anilines |
| CN101811973A (en) * | 2010-04-23 | 2010-08-25 | 浙江工业大学 | Method for synthesizing halogen aromatic amines by high-selectivity liquid phase hydrogenation under the condition of no solvent |
| CN103242168A (en) * | 2013-04-02 | 2013-08-14 | 淮安嘉诚高新化工股份有限公司 | Dehalogenation inhibitor |
| CN104163764A (en) * | 2014-08-07 | 2014-11-26 | 浙江工业大学 | Method for synthesising halogenated aromatic amine through hydrogenation in solvent-free condition |
Non-Patent Citations (2)
| Title |
|---|
| VALERICA PANDARUS 等: "A New Class of Heterogeneous Platinum Catalysts for the Chemoselective Hydrogenation of Nitroarenes", 《ADVANCED SYNTHESIS & CATALYSIS》 * |
| 张万生: "2,4-二氟苯胺的合成", 《辽宁化工》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115650859A (en) * | 2022-10-21 | 2023-01-31 | 利尔化学股份有限公司 | Preparation method of 2,4-difluoroaniline |
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