CN1634867A - Method for hydrogenation preparation of 4-amino-3-fluorophenol from o-fluoro-nitrobenzene and device therefor - Google Patents
Method for hydrogenation preparation of 4-amino-3-fluorophenol from o-fluoro-nitrobenzene and device therefor Download PDFInfo
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- CN1634867A CN1634867A CN 200310120860 CN200310120860A CN1634867A CN 1634867 A CN1634867 A CN 1634867A CN 200310120860 CN200310120860 CN 200310120860 CN 200310120860 A CN200310120860 A CN 200310120860A CN 1634867 A CN1634867 A CN 1634867A
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Abstract
The invention relates to hydrogenation preparation of 4-aminophenol from nitrobenzene, especially a method for hydrogenation preparation of 4-amino-3-fluorophenol from o-fluoro-nitrobenzene and device therefore. The reaction is carried out in autoclave with acid medium at 50-300C.,0.1-10.0MPa, and the stirring rate is 100-900 r/min, and the catalytically hydrogenated product is separated, distilled, filtered, and dried to prepare the product. O-fluoro nitrobenzene can be converted into 4-amino-3-fluobenzene by said method with conversion approaching 100%. 4-amino-3-fluobenzene is colourless crystallisate with selective around 92% and purity up to 99%. The catalytic process in the invention can be used for heterogeneous catalysis process of hydrogenation preparation of aminophenol from o-fluoro nitrobenzene and its substituted nitrobenzene.
Description
Technical field
The hydrogenation of chloronitrobenzene system of the present invention relates to 4-amino-phenol is the method and the device of o-fluoronitrobenzene hydrogenation system 4-amino-3-fluorophenol specifically.
Background technology
J.Chem.Soc.1964, p.473; U.S. Pat P4885389,3654365,4307249,6403833,5545754,3715397; European patent EP 0041837,0211545,0289297; Day disclosure special permission communique flat-182456 and clear-5373557; Chinese patent CN1038053, CN1061808, CN1087623, CN1077707, CN1105983, CN1237575, CN1121708 has only a United States Patent (USP) 5545754 and a day disclosure special permission communique flat-182456 and clear-5373557 to report that the Pt-C catalyzer is used for the shortening process of o-fluoronitrobenzene hydrogenation system 4-amino-3-fluorophenol, but do not report the effect of promotor, in addition, the Pt content of catalyst system therefor is up to 5wt.%.Other patent only relates to the catalyzer and the technological process of oil of mirbane system p-aminophenol.CN1237575 has described p-NP liquid-phase hydrogenatin reduction system p-aminophenol, comprises unit processes such as reduction, separation, crystallization, purification, drying.CN1121708 has reported a kind of purifying and preparation method of thick N-ethanoyl-p-aminophenol.
4-amino-3-fluorophenol is the intermediate of your type (flufenoxuron) sterilant benzoyl urea production of fluoro Fano Xu, can be used for the production of phenylium ester herbicide simultaneously, also can be used for 3,4,5,6-tetrahydro benzo pyrrolidone type weedicide and hair dye and kill the bacterial activity compound.The synthetic method of traditional 4-amino-3-fluorophenol is to carry out the azo reaction with the m-fluorophenol after the Sulphanilic Acid diazotization, feed 4-(2-fluoro-4-hydroxybenzene azo-group) Phenylsulfonic acid again, obtain after it is reduced in sodium bisulfite target product (J.Chem.Soc.1964, p.473).
The research work that oil of mirbane can be produced p-aminophenol through heterogeneous catalytic hydrogenation has many patent reports, as U.S. Pat P4885389,3654365,4307249,6403833,5545754,3715397, European patent EP 0041837,0211545,0289297.But relevant replacement p-aminophenol, for example the patent of o-fluoronitrobenzene hydrogenation production 4-amino-3-fluorophenol is less, have only U.S. Pat P5545754 to report 2,3-dichloronitrobenzene and 2-fluoro oil of mirbane generate 2 through shortening, 3-two chloro-4-amino-phenols and 4-amino-3-fluorophenol, with day disclosure special permission communique: flat-182456 and clear-5373557 have reported the manufacturing process of 4-amino-3-fluorophenol, adopt the Pt-C catalyst system in these production technique mostly, and its bullion content is up to 5% (weight).
Chinese patent CN1038053 and CN1061808 have reported the production method of oil of mirbane electroreduction legal system p-aminophenol.CN1087623 and CN1077707 have described the method that oil of mirbane and N-acetylize oil of mirbane is catalytically conveted to p-aminophenol and N-acetylize p-aminophenol at the shortening of noble metal catalyst respectively.CN1105983 has illustrated that zinc reduction is converted into oil of mirbane the technology of p-aminophenol.CN1237575 has described p-NP liquid-phase hydrogenatin reduction system p-aminophenol, comprises unit processes such as reduction, separation, crystallization, purification, drying.CN1121708 has reported that a kind of thick N-ethanoyl-p-aminophenol gets purifying and preparation method; but do not find as yet o-fluoronitrobenzene after shortening makes the thick mixed solution of 4-amino-3-fluorophenol how through extraction; separate; recrystallization; purify, drying repeats nonexpondable report to obtain high purity product and catalyzer.More than Bao Dao these catalytic hydrogenation reactions all carry out in the solution that contains tensio-active agent and/or water-soluble solvent, and after the reaction, catalyzer is difficult to separate from reaction system, recycles.
Summary of the invention
The object of the present invention is to provide method and device that a kind of catalyzer can reusable o-fluoronitrobenzene hydrogenation system 4-amino-3-fluorophenol.
For achieving the above object, the technical solution used in the present invention is:
The method of o-fluoronitrobenzene hydrogenation system 4-amino-3-fluorophenol, be reflected in the stainless steel high-pressure magnetic stirred autoclave that fills acidic medium and carry out, the consumption of acid is 1～10% of a reactant o-fluoronitrobenzene weight, adopt platinum/C catalyst, catalyst consumption is 2～5% of a reactant o-fluoronitrobenzene weight, before the reaction, feed inert gas and/or hydrogen to system, remove the air in the reactor, the temperature of reaction is 50～300 ℃, pressure is 0.1～10.0MPa, and stir speed (S.S.) is 100～900 rev/mins; The shortening product gets finished product through purge processes such as extracting and separating, distillation, suction filtration, washing and dryings.
Described platinum/C catalyst, the loading of platinum is 1～5% of a catalyst weight, is preferably 2wt%; Preferably contain Ti on the catalyzer and/or Mg makes auxiliary agent, the loading of auxiliary agent is 2～10% of a catalyst weight; Described o-fluoronitrobenzene can be analytical pure, chemical pure or industrial goods; Acid can be mineral acid or organic acid, as sulfuric acid, hydrochloric acid, formic acid, acetic acid etc.; The optimal reaction temperature of shortening is 70～150 ℃, and optimum response pressure is 0.3～3.0Mpa, and best stir speed (S.S.) is 300～600 rev/mins; The used extraction agent of purge process is an ester compound, as ethyl formate, and methyl acetate, ethyl acetate, propyl acetate, butylacetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl-butyrate, ethyl butyrate, propyl butyrate and/or butyl butyrate, best extraction agent is an ethyl formate, ethyl acetate, ethyl propionate, extraction temperature are 40～120 ℃, and best extraction temperature is 60～100 ℃; With the catalyzer filtering separation in the waste liquid of extraction back, so that reuse; In the purge process, the distillation of extraction liquid is first air distillation, underpressure distillation again, and the pressure of underpressure distillation is 0.01～0.09Mpa, best distillation pressure is 0.03～0.07Mpa; Then, with a spot of above-mentioned extraction agent washing repeatedly, more repeatedly with petroleum ether, suction filtration, recrystallization, more repeatedly with a spot of above-mentioned extraction agent washing, and more repeatedly with petroleum ether, suction filtration; Carry out vacuum-drying at last, promptly get purpose product 4-amino-3-fluorophenol, the exsiccant temperature is 30～100 ℃, and the optimum drying temperature is 40～80 ℃.
Described stainless steel high-pressure magnetic stirred autoclave, the inner liner polytetrafluoroethylene material.
The present invention has following advantage
1. catalyzer can be reused: catalytic hydrogenation reaction of the present invention carries out in the acidic medium that does not contain tensio-active agent, after the reaction, catalyzer can be separated from reaction system easily, recycles, reduce reaction cost widely, thereby improved economic benefit.Catalytic processes of the present invention also can be used for o-fluoronitrobenzene and other substituted-nitrobenzene hydrogenation and produces heterogeneous catalysis process for p-aminophenol.
2. high reactivity and highly selective: adopt catalytic production technology provided by the present invention and device, not only high reactivity and highly selective transform nitro in the o-fluoronitrobenzene amino, and the while is replaced by a hydroxyl at the contraposition aromatic ring hydrogen of amino, high productivity generates 4-amino-3-fluorophenol, the transformation efficiency of o-fluoronitrobenzene is near 100%, 4-amino-3-fluorophenol is the colourless crystallization thing, and selectivity is about 92%, and purity reaches 99%.
Description of drawings
Fig. 1 is o-fluoronitrobenzene hydrogenation system 4-amino-3-fluorophenol reaction unit synoptic diagram; 1 is hydrogen among the figure, and 2 is nitrogen, and 3 is stopping valve, and 4 is tensimeter, and 5 is voltage regulator, 6 is reducing valve, and 7 is purification pot, and 8 is strainer, and 9 is mass flowmeter, and 10 is check valve, 11 is magnetic stirring apparatus, and 12 is liner, and 13 is autoclave, and 14 are oil bath, and 15 is soap-foam flowmeter.
Embodiment
Below by example the present invention is described further.
As shown in Figure 1, the 500ml stainless steel cauldron 13 that has magnetic stirring apparatus 11 is placed in the oil bath 14, reactor 13 is provided with air inlet port and venting hole, be provided with the liner 12 of polytetrafluoroethylmaterial material in it, on the gas piping between sources of hydrogen 1 and the reactor 13, be provided with stopping valve 3, tensimeter 4, voltage regulator 5, purification pot 7, strainer 8, mass flowmeter 9 and check valve 10; On the gas piping between source nitrogen 2 and the reactor 13, be provided with stopping valve 3, reducing valve 6 and purification pot 7; With exhaust line that reactor 13 venting holes link to each other on be provided with tensimeter 4 and 15 and be soap-foam flowmeter.
In reactor 13, add 10.8 gram o-fluoronitrobenzenes respectively, the 173ml deionized water, 7.7ml dehydrated alcohol, the 10.4 gram vitriol oils, 0.426 gram platinum carrying capacity is the 2wt.%Pt-C catalyzer, temperature of reaction is 90 ℃, pressure is 0.65MPa, and stir speed (S.S.) is 400 rev/mins, and it is zero reacting to hydrogen flowing quantity.The hydrogenation reaction product mixed solution that obtains adds extraction heat three times with the 50ml ethyl acetate earlier, and underpressure distillation is carried out in 80 ℃ of heating in water bath air distillations then, and pressure is-0.05MPa to cool off the back suction filtration again.Amount of ethyl acetate washing repeatedly, the sherwood oil boiling washing repeatedly, last suction filtration, and carry out vacuum-drying, drying temperature is about 60 ℃.Get the colourless crystallization thing and be 4-amino-3-fluorophenol product, purity reaches more than 99%.
Embodiment 2
It is identical with example 1 that temperature of reaction changes 80 ℃ of other conditions into, and other step is with example 1.
It is identical with example 1 that temperature of reaction changes 100 ℃ of other conditions into, and other step is with example 1.
It is identical with example 1 that temperature of reaction changes 120 ℃ of other conditions into, and other step is with example 1.
Reaction pressure changes 0.40MPa into, and other condition is identical with example 1, and other step is with example 1.
Reaction pressure changes 0.90MPa into, and other condition is identical with example 1, and other step is with example 1.
Reaction pressure changes 1.20MPa into, and other condition is identical with example 1, and other step is with example 1.
It is 500 rev/mins that reaction changes stir speed (S.S.) into, and other condition is identical with example 1, and other step is with example 1.
It is 600 rev/mins that reaction changes stir speed (S.S.) into, and other condition is identical with example 1, and other step is with example 1.
It is 800 rev/mins that reaction changes stir speed (S.S.) into, and other condition is identical with example 1, and other step is with example 1.
O-fluoronitrobenzene hydrogenation system 4-amino-3-fluorophenol that table 1 has been listed the 2wt.%Pt-C catalyzer gets the reaction evaluating result under different condition
*
| Example | ??1 | ??2 | ??3 | ??4 | ??5 | ??6 | ??7 |
| ??S C6H6NF | ??9.4 | ??9.8 | ??9.6 | ??9.5 | ??7.6 | ??7.9 | ??7.5 |
| ??S C6H6NOF | ??90.6 | ??90.1 | ??90.4 | ??90.2 | ??92.4 | ??92.1 | ??92.5 |
| Example | ??8 | ??9 | ??10 | ||||
| ??S C6H6NF | ??9.0 | ??10.5 | ??10.2 | ||||
| ??S C6H6NOF | ??91.0 | ??89.5 | ??89.5 |
*The transformation efficiency of o-fluoronitrobenzene is all near 100%.S
C6H6NFBe adjacent fluoroaniline selectivity, S
C6H6NOFBe 4-amino-3-fluorophenol selectivity.
Claims (10)
- The method of 1 one kinds of o-fluoronitrobenzene hydrogenation system 4-amino-3-fluorophenols, it is characterized in that: be reflected in the autoclave that fills acidic medium and carry out, the consumption of acid is 1～10% of a reactant o-fluoronitrobenzene weight, adopt platinum/C catalyst, catalyst consumption is 2～5% of a reactant o-fluoronitrobenzene weight, the temperature of reaction is 50～300 ℃, and pressure is 0.1～10.0MPa, and stir speed (S.S.) is 100～900 rev/mins; The shortening product is through extracting and separating, distillation, filtration, the dry finished product that gets.
- 2. according to the method for the described o-fluoronitrobenzene of claim 1 hydrogenation system 4-amino-3-fluorophenol, it is characterized in that: described platinum/C catalyst, make auxiliary agent with Ti and/or Mg, the loading of auxiliary agent is 2～10% of a catalyst weight content, and the loading of platinum is 1～5% of a catalyst weight content.
- 3. according to the method for the described o-fluoronitrobenzene of claim 1 hydrogenation system 4-amino-3-fluorophenol, it is characterized in that: the extraction agent of described extracting and separating is a methyl acetate, ethyl acetate, propyl acetate, butylacetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl-butyrate, ethyl butyrate, propyl butyrate and/or butyl butyrate ester compound, extraction temperature are 40～120 ℃.
- 4. according to the method for the described o-fluoronitrobenzene of claim 3 hydrogenation system 4-amino-3-fluorophenol, it is characterized in that: extraction agent is an ethyl formate, ethyl acetate and/or ethyl propionate, and extraction temperature is 60～100 ℃.
- 5. according to the method for the described o-fluoronitrobenzene of claim 1 hydrogenation system 4-amino-3-fluorophenol, it is characterized in that: described distillation is air distillation and underpressure distillation, and the pressure of underpressure distillation is 0.01～0.09Mpa.
- 6. according to the method for the described o-fluoronitrobenzene of claim 5 hydrogenation system 4-amino-3-fluorophenol, it is characterized in that: the pressure of underpressure distillation is 0.03～0.07Mpa.
- 7. according to the method for the described o-fluoronitrobenzene of claim 1 hydrogenation system 4-amino-3-fluorophenol, it is characterized in that: described drying temperature is 30～100 ℃.
- 8. according to the method for the described o-fluoronitrobenzene of claim 1 hydrogenation system 4-amino-3-fluorophenol, it is characterized in that: the temperature of reaction of shortening is 70～150 ℃, and reaction pressure is 0.3～3.0Mpa, and stir speed (S.S.) is 300～600 rev/mins.
- 9. according to the method for the described o-fluoronitrobenzene of claim 1 hydrogenation system 4-amino-3-fluorophenol, it is characterized in that: reactor is a stainless steel high-pressure magnetic stirred autoclave, is lined with polytetrafluoroethylmaterial material in it.
- 10. the isolated plant of the described o-fluoronitrobenzene of claim 1 hydrogenation system 4-amino-3-fluorophenol is characterized in that: comprise the reactor (13) that has magnetic stirring apparatus (11), oil bath (14), sources of hydrogen (1) and source nitrogen (2); Reactor (13) is provided with air inlet port and venting hole, sources of hydrogen (1) and source nitrogen (2) are connected with air inlet port pipeline on the reactor (13) respectively, on the admission passage between sources of hydrogen (1) and the reactor (13), be provided with pressure-regulator (5) successively, purification pot (7), strainer (8), mass flowmeter (9); On the admission passage between source nitrogen (2) and the reactor (13), be provided with reducing valve (6) and purification pot (7) successively.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200310120860 CN1634867A (en) | 2003-12-30 | 2003-12-30 | Method for hydrogenation preparation of 4-amino-3-fluorophenol from o-fluoro-nitrobenzene and device therefor |
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| CN 200310120860 CN1634867A (en) | 2003-12-30 | 2003-12-30 | Method for hydrogenation preparation of 4-amino-3-fluorophenol from o-fluoro-nitrobenzene and device therefor |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030616A (en) * | 2010-09-17 | 2011-04-27 | 上海赫腾精细化工有限公司 | Preparation method for 2,3,5,6-tetrafluorohydroquinone |
| CN106854006A (en) * | 2016-12-21 | 2017-06-16 | 华南理工大学 | The extractant and extracting process of a kind of efficient removal COD and polyhydric phenols |
| WO2017125941A1 (en) * | 2016-01-18 | 2017-07-27 | Natco Pharma Ltd | An improved process for the preparation of regorafenib |
| CN108929235A (en) * | 2018-07-19 | 2018-12-04 | 苏州盖德精细材料有限公司 | A kind of high-efficiency synthesis method of 4- amino -3- fluorophenol |
| CN114656365A (en) * | 2022-03-07 | 2022-06-24 | 西安瑞联新材料股份有限公司 | Method for preparing 2-fluoro-4-hydroxyaniline |
| CN115557858A (en) * | 2022-10-20 | 2023-01-03 | 淮安晶彩新材料科技有限公司 | Method for synthesizing 2-fluoro-4-aminophenol |
-
2003
- 2003-12-30 CN CN 200310120860 patent/CN1634867A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030616A (en) * | 2010-09-17 | 2011-04-27 | 上海赫腾精细化工有限公司 | Preparation method for 2,3,5,6-tetrafluorohydroquinone |
| WO2017125941A1 (en) * | 2016-01-18 | 2017-07-27 | Natco Pharma Ltd | An improved process for the preparation of regorafenib |
| CN106854006A (en) * | 2016-12-21 | 2017-06-16 | 华南理工大学 | The extractant and extracting process of a kind of efficient removal COD and polyhydric phenols |
| CN106854006B (en) * | 2016-12-21 | 2020-08-18 | 华南理工大学 | Extracting agent for efficiently removing COD (chemical oxygen demand) and polyphenol and extracting method |
| CN108929235A (en) * | 2018-07-19 | 2018-12-04 | 苏州盖德精细材料有限公司 | A kind of high-efficiency synthesis method of 4- amino -3- fluorophenol |
| CN114656365A (en) * | 2022-03-07 | 2022-06-24 | 西安瑞联新材料股份有限公司 | Method for preparing 2-fluoro-4-hydroxyaniline |
| CN115557858A (en) * | 2022-10-20 | 2023-01-03 | 淮安晶彩新材料科技有限公司 | Method for synthesizing 2-fluoro-4-aminophenol |
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