CN105418439A - Method and device for producing 3-chlorine-4-fluoroaniline - Google Patents
Method and device for producing 3-chlorine-4-fluoroaniline Download PDFInfo
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- CN105418439A CN105418439A CN201510787946.1A CN201510787946A CN105418439A CN 105418439 A CN105418439 A CN 105418439A CN 201510787946 A CN201510787946 A CN 201510787946A CN 105418439 A CN105418439 A CN 105418439A
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- fluoroaniline
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- dichloronitrobenzene
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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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
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Abstract
The invention relates to the technical field of chemical industry production and particularly discloses a method and device for producing 3-chlorine-4-fluoroaniline. The method for producing 3-chlorine-4-fluoroaniline adopts 3,4-dichloronitrobenzene as a raw material and is characterized in that 3,4-dichloronitrobenzene, anhydrous potassium fluoride and a phase transfer catalyst are added to a fluorination kettle, and 3-chlorine-4-fluoronitrobenzene is directly generated; 3-chlorine-4-fluoronitrobenzene is washed, and byproducts, namely, potassium chloride and potassium fluoride are dissolved in water to be completely washed; a 1% platinum-carbon catalyst is adopted in a treated crude product to directly react with hydrogen in a hydrogenation kettle to generate crude 3-chlorine-4-fluoroaniline in a reducing mode, and then the product is obtained after vacuum distillation. The whole technological process is short, operation is easy, the automatic control level is high, and the product yield is high. No flux needs to be added to a reactant, the utilization rate of the hydrogenation kettle is increased, a solvent rectification device is omitted, production cost is reduced, and the method and device are suitable for wide application and popularization.
Description
(1) technical field
The present invention relates to chemical production field, particularly a kind of method and device producing the chloro-4-fluoroaniline of 3-.
(2) background technology
The fluorine fine chemicals industries such as fluorine-containing medicines, agricultural chemicals and intermediate thereof, fluorinated liquid crystal material are more special industries, being three medicines (medicine, agricultural chemicals, veterinary drug) of domestic and international focus development and the key of the great science and technology of novel material and industrialization engineering, is one of strategic emphasis of national development.In country's " 12 " development program, fluorine chemical is single-row is an ad hoc planning, " 12 " period will give priority to fluoride-containing PMMA, plan increased value 1,200 hundred million yuan, average annual growth by 15%, and fluorine fine chemicals is positioned at fluorine chemical industrial chain most significant end, its average growth rate per annum reaches more than 30%, and the market space is huge.3-chloro-4-fluoroaniline is that synthesis various new, efficient, serial antibacterials of wide spectrum are as the important intermediate of the quinolones such as Norxin, Zanocin, Ciprofloxacin, the acid of fluorine chlorine piperazine and derivative drugs thereof, it is the basic product of third generation quinolones, also be the basic material of sterilant, fluoro-containing pesticide weedicide 4-fluorobenzene as chloro-in 3-fluoroacetic acid etc., market purposes is boundless.The shortcomings such as the chloro-4-fluoroaniline of current domestic production 3-exists technique and falls behind, and the technological process of production is long, product hand greenery patches, and production cost is high, can not meet the market requirement.
(3) summary of the invention
The present invention, in order to make up the deficiencies in the prior art, provides that a kind of technological operation is simple, level of automation is high, the method for the chloro-4-fluoroaniline of the production 3-that production cost is low and device.
The present invention is achieved through the following technical solutions:
Produce a method for the chloro-4-fluoroaniline of 3-, with 3,4-dichloronitrobenzene for raw material, comprise the steps:
(1) 3,4-dichloronitrobenzene, anhydrous potassium fluoride and phase-transfer catalyst are joined and fluoridize in still, when making solvent without dimethyl sulfoxide (DMSO), temperature of reaction controls at 140-150 DEG C, directly generates the chloro-4-fluoronitrobenzene of 3-under pressure 0-0.05MPa condition;
(2) side product chlorinated potassium and Potassium monofluoride to be dissolved in water through washing and all to wash by 3-chloro-4-fluoronitrobenzene;
(3) the content in crude product 98-99% after process, without the need to rectifying, adopts 1% platinum carbon catalyst to generate 3-chloro-4-fluoroaniline crude product without direct under the condition of methanol solvate and hydrogen reaction reduction in hydriding reactor, obtains product through rectification under vacuum.
In the present invention, 3,4-dichloronitrobenzene and Potassium monofluoride produce 3-chloro-4-fluoronitrobenzene mixed solution according to certain proportioning fluoridizing in still to fluoridize, by-product Repone K is removed through washing kettle, crude product after washing shortening in hydrogenation still produces 3-chloro-4-fluoroaniline crude product, produces qualified product through rectification under vacuum.
Its preferred technical scheme is:
In step (1), the mass ratio of 3,4-dichloronitrobenzene and anhydrous potassium fluoride is the mass ratio of 1:1.2-1.25,3,4-dichloronitrobenzene and phase-transfer catalyst is 1:0.06-0.07.
In step (2), the Repone K after washing is for the production of salt of wormwood.
In step (3), hydriding reactor interior reaction temperature is 70 ± 5 DEG C, and reaction pressure is 0.6 ± 1MPa; Hydriding reactor adds anti-dechlorination inhibitor before feeding intake, and guarantees that reaction back end hydrogenation dechlorination amount controls below thousandth, solves in reaction process because serious dechlorination causes the corrosion to equipment; 5m
3hydriding reactor charging capacity be 3m
3; In hydrogenation process, by purpose ceramic-film filter separating catalyst; Wherein, filtration and the regeneration of described strainer are all carried out under pressure-fired, and filter type is chimney filter inner filtration, use hydrogen to reuse bottom the blowback to hydriding reactor of strainer inner catalyst, reduce hydrogen consumption.
Realize the device of aforesaid method, comprise and fluoridize still, it is characterized in that: described in fluoridize bottom still and be connected with washing kettle, washing kettle outlet is upper is communicated with crude product groove, and crude product groove connects hydriding reactor by product pump, hydriding reactor is provided with the strainer that piping loop connects.
Described strainer connects hydrogenation liquid storage tank.
Described fluoridize still top outlet be connected with material recycle condenser, fluoridize still and be provided with external jacket, thief hole and whipping appts; Described hydriding reactor is provided with external jacket, inner coil pipe, thief hole and self-absorbing type stirrer.Agitator is in order to improve chlorination reaction velocity, and external jacket then can realize the heating and cooling to material, guarantees to react safe operation, and thief hole is convenient to sampling analysis.
The present invention adopts phase-transfer catalyst and platinum carbon catalyst, and fluoridize and hydrogenation mild condition, whole technical process is short, simple to operate, and automatic control level is high, and product yield is high; Without the need to adding flux in reactant, improve the utilization ratio of hydriding reactor, saving solvent distillation device, reducing production cost, being suitable for wide popularization and application.
(4) accompanying drawing explanation
Below in conjunction with accompanying drawing, the present invention is further illustrated.
Fig. 1 is structural representation of the present invention.
In figure, 1 fluoridizes still, 2 condensers, 3 washing kettles, 4 crude product grooves, 5 product pumps, 6 hydriding reactors, 7 strainers.
(5) embodiment
Accompanying drawing is a kind of specific embodiment of the present invention.This embodiment comprises fluoridizes still 1, described in fluoridize bottom still 1 and be connected with washing kettle 3, washing kettle 3 exports and is above communicated with crude product groove 4, and crude product groove 4 connects hydriding reactor 6 by product pump 5, hydriding reactor 6 is provided with the strainer 7 that piping loop connects; Described strainer 7 connects hydrogenation liquid storage tank; Described fluoridize still 1 top outlet be connected with material recycle condenser 2, fluoridize still 1 and be provided with external jacket, thief hole and whipping appts; Described hydriding reactor 6 is provided with external jacket, inner coil pipe, thief hole and self-absorbing type stirrer.
By 3,4-dichloronitrobenzene and anhydrous potassium fluoride are according to mass ratio 1:1.2-1.25,3,4-dichloronitrobenzene and phase-transfer catalyst consumption are that mass ratio 1:0.06-0.07 joins and fluoridizes in still 1, when making solvent without DMSO, temperature of reaction controls at 140-150 DEG C, and under pressure 0-0.05MPa condition, 3,4-DCA and Potassium monofluoride direct reaction generate the chloro-4-fluoronitrobenzene of 3-.By-product Repone K and a small amount of Potassium monofluoride to be dissolved in water through washing and all to wash by 3-chloro-4-fluoronitrobenzene in washing kettle 3, and the Klorvess Liquid 10-15% after washing is for generating salt of wormwood.Content in crude product 98%-99% after process, without the need to rectifying, adopts novel 1%Pt/c at 5m
3hydriding reactor 6 in without under the condition of methanol solvate directly and hydrogen reaction reduction reaction generation 3-chloro-4-fluoroaniline crude product, hydriding reactor 6 reactor control temperature 70 ± 5 DEG C, reaction pressure 0.6 ± 1MPa, a charging capacity 3m
3.Crude product after hydrogenation is through the qualified product of rectification under vacuum extraction; Catalyzer is filtered by strainer 7, and clear liquid enters into subsequent processing.Catalyzer again returns in hydriding reactor 6 and reuses.Whole technological reaction mild condition, solvent-free purification process, shortens technical process.
Claims (9)
1. produce the method for the chloro-4-fluoroaniline of 3-for one kind, with 3,4-dichloronitrobenzene is raw material, it is characterized by, comprise the steps: that (1) is by 3,4-dichloronitrobenzene, anhydrous potassium fluoride and phase-transfer catalyst join to be fluoridized in still, and temperature of reaction controls at 140-150 DEG C, directly generates the chloro-4-fluoronitrobenzene of 3-under pressure 0-0.05MPa condition; (2) side product chlorinated potassium and Potassium monofluoride to be dissolved in water through washing and all to wash by 3-chloro-4-fluoronitrobenzene; (3) crude product after process adopts 1% platinum carbon catalyst, and in hydriding reactor, direct and hydrogen reaction reduction generation 3-chloro-4-fluoroaniline crude product, then obtains product through rectification under vacuum.
2. the method for the chloro-4-fluoroaniline of production 3-according to claim 1, it is characterized in that: in step (1), the mass ratio of 3,4-dichloronitrobenzene and anhydrous potassium fluoride is 1:1.2-1.25, the mass ratio of 3,4-dichloronitrobenzene and phase-transfer catalyst is 1:0.06-0.07.
3. the method for the chloro-4-fluoroaniline of production 3-according to claim 1, is characterized in that: in step (2), the Repone K after washing is for the production of salt of wormwood.
4. the method for the chloro-4-fluoroaniline of production 3-according to claim 1, it is characterized in that: in step (3), hydriding reactor interior reaction temperature is 70 ± 5 DEG C, and reaction pressure is 0.6 ± 1MPa; Hydriding reactor adds anti-dechlorination inhibitor before feeding intake, in hydrogenation process, by purpose ceramic-film filter separating catalyst.
5. the method for the chloro-4-fluoroaniline of production 3-according to claim 4, it is characterized in that: filtration and the regeneration of described strainer are all carried out under pressure-fired, filter type is chimney filter inner filtration, uses hydrogen to reuse bottom the blowback to hydriding reactor of strainer inner catalyst.
6. realize the device of method described in claim 1, comprise and fluoridize still (1), it is characterized in that: described in fluoridize still (1) bottom be connected with washing kettle (3), washing kettle (3) outlet is communicated with crude product groove (4), crude product groove (4) connects hydriding reactor (6) by product pump (5), hydriding reactor (6) is provided with the strainer (7) that piping loop connects.
7. device according to claim 5, is characterized in that: described strainer (7) connects hydrogenation liquid storage tank.
8. device according to claim 5, is characterized in that: described in fluoridize still (1) top outlet be connected with material recycle condenser (2), fluoridize still (1) and be provided with external jacket, thief hole and whipping appts.
9. device according to claim 5, is characterized in that: described hydriding reactor (6) is provided with external jacket, inner coil pipe, thief hole and self-absorbing type stirrer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201510787946.1A CN105418439A (en) | 2015-11-17 | 2015-11-17 | Method and device for producing 3-chlorine-4-fluoroaniline |
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| CN201510787946.1A CN105418439A (en) | 2015-11-17 | 2015-11-17 | Method and device for producing 3-chlorine-4-fluoroaniline |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108997135A (en) * | 2018-07-18 | 2018-12-14 | 张金河 | A kind of method and device producing the chloro- 4- fluoroaniline of 3- |
| CN109369414A (en) * | 2018-11-15 | 2019-02-22 | 江苏中旗科技股份有限公司 | A method of preparing the chloro- 2,4 difluorobenzene amine of Teflubenzuron intermediate 3,5- bis- |
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| CN1515542A (en) * | 2003-08-28 | 2004-07-28 | 解卫宇 | Method for co-production of 3-chloro-4-fluoroaniline and 2, 6-dichlorofluorobenzene |
| WO2013182665A2 (en) * | 2012-06-08 | 2013-12-12 | Evonik Industries Ag | Use of thermally-treated supported cobalt catalysts for hyrogenating aromatic nitro compounds |
| CN104292113A (en) * | 2014-03-04 | 2015-01-21 | 多氟多化工股份有限公司 | Preparation method of 3-chloro-4-fluoroaniline |
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2015
- 2015-11-17 CN CN201510787946.1A patent/CN105418439A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1515542A (en) * | 2003-08-28 | 2004-07-28 | 解卫宇 | Method for co-production of 3-chloro-4-fluoroaniline and 2, 6-dichlorofluorobenzene |
| WO2013182665A2 (en) * | 2012-06-08 | 2013-12-12 | Evonik Industries Ag | Use of thermally-treated supported cobalt catalysts for hyrogenating aromatic nitro compounds |
| CN104292113A (en) * | 2014-03-04 | 2015-01-21 | 多氟多化工股份有限公司 | Preparation method of 3-chloro-4-fluoroaniline |
Non-Patent Citations (1)
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| 王尔华: "3-氯-4-氟苯胺的合成改进法", 《中国药科大学学报》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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- |
| CN108997135A (en) * | 2018-07-18 | 2018-12-14 | 张金河 | A kind of method and device producing the chloro- 4- fluoroaniline of 3- |
| CN109369414A (en) * | 2018-11-15 | 2019-02-22 | 江苏中旗科技股份有限公司 | A method of preparing the chloro- 2,4 difluorobenzene amine of Teflubenzuron intermediate 3,5- bis- |
| CN109369414B (en) * | 2018-11-15 | 2020-04-10 | 江苏中旗科技股份有限公司 | Method for preparing teflubenzuron intermediate 3, 5-dichloro-2, 4-difluoroaniline |
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