CN106748830A - A kind of preparation method of the fluorophenol of 3 amino 4 - Google Patents
A kind of preparation method of the fluorophenol of 3 amino 4 Download PDFInfo
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- CN106748830A CN106748830A CN201710111717.7A CN201710111717A CN106748830A CN 106748830 A CN106748830 A CN 106748830A CN 201710111717 A CN201710111717 A CN 201710111717A CN 106748830 A CN106748830 A CN 106748830A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/10—Separation; Purification; Stabilisation; Use of additives
Abstract
The invention provides a kind of preparation method of the fluorophenol of 3 amino 4, comprise the following steps：The nitrobenzene oxygen Ethyl formate of 2 bromine, 4 fluorine 5, alkaline matter, hydrogenation catalyst and organic solvent are mixed, mixture is obtained；Hydrogenation reaction is carried out to being passed through hydrogen in the mixture in confined conditions, obtains the fluorophenol of 3 amino 4；It is described to be passed through the air discharge in enclosed system before hydrogen.The preparation method synthetic route that the present invention is provided is short, step is few, and single step reaction is only needed from the nitrobenzene oxygen Ethyl formate of 2 bromine, the 4 fluorine 5 synthesis fluorophenol of 3 amino 4, and the three wastes that course of reaction is produced are few, synthetic product simple separation is that can obtain the product that purity reaches more than 99%, high income.
Description
Technical field
The present invention relates to the technical field of organic synthesis, more particularly to a kind of preparation method of 3- amino-4-fluorophenols.
Background technology
3- amino-4-fluorophenols are the important intermediates of synthetic pesticide insecticide flufenoxuron, can be also used for synthesis medicine
Compound and liquid-crystal compounds, it is also possible to for producing hair dye and antibacterial activity agent, have in organic synthesis field important
Application value.
In the art, the conventional synthetic method of 3- amino-4-fluorophenols can be represented by following reaction equations：
The method synthesizes the 2- fluoro- 5- nitrobenzene oxygen first of bromo- 4- with p-fluorophenol as raw material by bromination, esterification and nitration reaction
Acetoacetic ester, then reduces the generation 2- fluoro- 5- aminobenzenes oxygen Ethyl formates of bromo- 4-, in zinc powder and hydrogen after separation in acid medium
Dehalogenation, hydrolysis and acidifying, are recrystallized to give 3- amino-4-fluorophenols afterwards in sodium hydroxide solution.
Above-mentioned preparation method needs two steps from the fluoro- 5- nitrobenzene oxygen Ethyl formate synthesis 3- amino-4-fluorophenols of the bromo- 4- of 2-
Reaction, by the fluoro- 5- aminobenzenes oxygen Ethyl formate reduction generation 2- fluoro- 5- aminobenzenes of bromo- 4- of the bromo- 4- of 2- first in acid medium
Oxygen Ethyl formate, the step wastewater flow rate is big, and product needs to separate, and causes yield relatively low；The fluoro- 5- aminobenzenes oxygen first of the bromo- 4- of 2-
Acetoacetic ester needs a large amount of zinc powders to carry out dehalogenation, hydrolysis and be acidified in sodium hydroxide solution, and the step equally produces substantial amounts of useless
Gu and waste liquid, be unfavorable for environmental protection.And the method post processing is cumbersome, product needed recrystallization can just obtain purity 3- ammonia higher
Base -4- fluorophenols, cause yield relatively low, from the fluoro- 5- nitrobenzene oxygen Ethyl formate synthesis 3- amino-4-fluorophenols of the bromo- 4- of 2-
The total recovery of two-step reaction is only 76% or so.
The content of the invention
In view of this, present invention aim at providing, a kind of step is few, energy consumption is low, the three wastes are few, target product purity is high, anti-
Answer the preparation method of the 3- amino-4-fluorophenols of high income.
In order to realize foregoing invention purpose, the present invention provides following technical scheme：
The invention provides a kind of preparation method of 3- amino-4-fluorophenols, comprise the following steps：
The fluoro- 5- nitrobenzene oxygen Ethyl formates of the bromo- 4- of 2-, alkaline matter, hydrogenation catalyst and organic solvent are mixed, is obtained
Mixture；
Hydrogenation reaction is carried out to being passed through hydrogen in the mixture in confined conditions, obtains 3- amino-4-fluorophenols；Institute
State and discharge the air in enclosed system before being passed through hydrogen.
Preferably, the alkaline matter is inorganic base and/or organic amine.
Preferably, the inorganic base mixing for one or more in sodium carbonate, potassium carbonate, NaOH and potassium hydroxide
Compound.
Preferably, the organic amine is one or more in ethamine, triethylamine, propylamine, 1,3- propane diamine and butylamine
Mixture.
Preferably, the hydrogenation catalyst is palladium carbon and/or Raney's nickel.
Preferably, the organic solvent is the mixture of one or more in methyl alcohol, ethanol, ethyl acetate and toluene.
Preferably, the temperature of the hydrogenation reaction is 30~60 DEG C；The initial pressure of the hydrogenation reaction be 1.0~
Hydrogen to initial pressure is added in 2.0MPa, pressure drop when being more than 0.5MPa, reacted to hydrogen is not inhaled.
Preferably, the mol ratio of the fluoro- 5- nitrobenzene oxygen Ethyl formates of the bromo- 4- of the 2- and alkaline matter is 1:3~6；Institute
The mass ratio for stating hydrogenation catalyst and the fluoro- 5- nitrobenzene oxygen Ethyl formates of the bromo- 4- of 2- is 0.05~0.15:1.
Preferably, the mass ratio of the organic solvent and the fluoro- 5- nitrobenzene oxygen Ethyl formates of the bromo- 4- of 2- is 4~10:1.
Preferably, also separated including product after the hydrogenation reaction, the product is separated and comprised the following steps：
Reacting liquid filtering is removed into hydrogenation catalyst, filtrate is obtained；
By filtrate distillation, solid matter is obtained；
By solid matter washing, filter and dry, obtain 3- amino-4-fluorophenols.
The invention provides a kind of preparation method of 3- amino-4-fluorophenols, comprise the following steps：By the fluoro- 5- of the bromo- 4- of 2-
The mixing of nitrobenzene oxygen Ethyl formate, alkaline matter, hydrogenation catalyst and organic solvent, obtains mixture；To being passed through in mixture
Hydrogen is reacted, and obtains 3- amino-4-fluorophenols.The preparation method synthetic route that the present invention is provided is short, and step is few, from 2-
The bromo- fluoro- 5- nitrobenzene oxygen Ethyl formate synthesis 3- amino-4-fluorophenols of 4- only need only to be needed in single step reaction, and production process
Organic solvent eliminates acid medium and reduces the step of with zinc powder dehalogenation as reaction medium, and whole production process only produces few
The waste liquid of amount, environmentally friendly, the product purity for obtaining is high, high income.
Further, the synthetic product of the preparation method that the present invention is provided is without further purifying, it is only necessary to simple solid-liquid point
From the product that can obtain high-purity.Experiment shows that the 3- amino-4-fluorophenols that the preparation method that the present invention is provided is obtained need not
Purifying purity is that can reach more than 99%, and yield is 90% or so.
Specific embodiment
The invention provides a kind of preparation method of 3- amino-4-fluorophenols, comprise the following steps：
The fluoro- 5- nitrobenzene oxygen Ethyl formates of the bromo- 4- of 2-, alkaline matter, hydrogenation catalyst and organic solvent are mixed, is obtained
Mixture；
Hydrogenation reaction is carried out to being passed through hydrogen in the mixture in confined conditions, obtains 3- amino-4-fluorophenols；Institute
State and discharge the air in enclosed system before being passed through hydrogen.
The present invention mixes the fluoro- 5- nitrobenzene oxygen Ethyl formates of the bromo- 4- of 2-, alkaline matter, hydrogenation catalyst and organic solvent
Close, obtain mixture.In the present invention, the alkaline matter is preferably inorganic base and/or organic amine；The inorganic base is preferably
The mixture of one or more in sodium carbonate, potassium carbonate, NaOH and potassium hydroxide, more preferably sodium carbonate or carbonic acid
Potassium；The organic amine is preferably the mixture of one or more in ethamine, triethylamine, propylamine, 1,3- propane diamine and butylamine；More
Preferably ethamine and/or triethylamine.
In the present invention, the hydrogenation catalyst is preferably palladium carbon and/or Raney's nickel, more preferably palladium carbon；The present invention is right
The no particular/special requirement in source of hydrogenation catalyst, uses commodity commercially.
In the present invention, the organic solvent is preferably one or more in methyl alcohol, ethanol, ethyl acetate and toluene
Mixture, more preferably methyl alcohol or ethanol；The mixture of the organic solvent is preferably 2~3 kinds of mixtures of organic solvent, more
The preferably mixture or methyl alcohol and the mixture of toluene of methyl alcohol and ethanol；Methyl alcohol and second in the mixture of the methyl alcohol and ethanol
The volume ratio of alcohol is preferably 1~1.2:1, more preferably 1.05~1.1:1；Methyl alcohol and first in the mixture of the methyl alcohol and toluene
The volume ratio of benzene is preferably 1~1.2:1, more preferably 1.05~1.1:1.
In the present invention, the mol ratio of the fluoro- 5- nitrobenzene oxygen Ethyl formates of the bromo- 4- of the 2- and alkaline matter is preferably 1:
3~6, more preferably 1:4~5；The mass ratio of the hydrogenation catalyst and the fluoro- 5- nitrobenzene oxygen Ethyl formates of the bromo- 4- of 2- is preferred
It is 0.05~0.15:1, more preferably 0.08~0.12:1, most preferably 0.1:1；The organic solvent and the fluoro- 5- of the bromo- 4- of 2-
The mass ratio of nitrobenzene oxygen Ethyl formate is preferably 4~10:1, more preferably 5~8:1, most preferably 6~7:1.
The no particular/special requirement in source of the present invention fluoro- 5- nitrobenzene oxygen Ethyl formates of 4- bromo- to 2-, uses the normal of this area
Rule method is synthesized.In the art, generally with p-fluorophenol as starting material, by bromination, three steps of esterification and nitrification
Reaction, synthesizes the 2- fluoro- 5- nitrobenzene oxygen Ethyl formates of bromo- 4-, and reaction equation is as shown in Equation 1：
After obtaining mixture, the present invention carries out hydrogenation reaction to being passed through hydrogen in the mixture in confined conditions, obtains
To 3- amino-4-fluorophenols；It is described to be passed through the air discharge in enclosed system before hydrogen.The present invention preferably passes through inert gas
The method of displacement discharges the air in enclosed system, and the inert gas is preferably nitrogen, argon gas and helium, more preferably nitrogen
Gas；The present invention does not have particular/special requirement to the method for specific displaced air, uses the conventional method of replacing in this area.
In the present invention, the temperature of the hydrogenation reaction is preferably 30~60 DEG C, more preferably 40~50 DEG C；The hydrogenation
The initial pressure of reaction is preferably 1.0~2.0MPa, more preferably 1.3~1.8MPa；The present invention is preferably more than in pressure drop
Hydrogen to initial pressure is added during 0.5MPa.In the present invention, the hydrogenation reaction is preferred reacts to hydrogen is not inhaled, overall reaction
Time is preferably 5~8h, more preferably 6~7h.
The present invention does not have particular/special requirement to the speed for being passed through hydrogen, in the particular embodiment, can be according to reactor
The volume of size and mixture adjusts the speed that is passed through of hydrogen, and the present invention preferably makes in kettle by controlling hydrogen to be passed through speed
Rate of pressure rise is controlled in 0.3~0.8MPa/min, more preferably 0.5MPa/min；Preferably logical hydrogen of the invention extremely reacts
Stop being passed through for hydrogen after beginning pressure, pressure in kettle is observed during the course of the reaction, hydrogen is added extremely when pressure drop is more than 0.5MPa
Initial pressure.
The present invention preferably carries out hydrogen abstraction reaction under agitation, the speed of the stirring be preferably 300~500 turns/
Min, more preferably 350~450 turns/min.The present invention does not have special limitation to the hydrogenation reaction equipment, using ability
Autoclave known to field technique personnel.
In some embodiments of the invention, can at normal temperatures by the fluoro- 5- nitrobenzene oxygen formic acid second of the bromo- 4- of 2-
Ester, alkaline matter, hydrogenation catalyst and organic solvent are added in reactor, are then sealed reactor, with nitrogen displacement 3~
5 times, make the air emptying in reactor, backward reactor in be passed through in hydrogen to kettle pressure be 1.0~2.0MPa, and heat up
To reaction temperature, hydrogen abstraction reaction is carried out under agitation, add hydrogen to initial pressure when pressure drop is more than 0.5MPa, repeatedly
Operation is until reaction to hydrogen is not inhaled.
After the completion of the hydrogen abstraction reaction, product is preferably carried out separation of solid and liquid by the present invention, obtains 3- amino-4-fluorophenols.
The present invention is preferably separated product by following steps：
Reacting liquid filtering is removed into hydrogenation catalyst, filtrate is obtained；
By filtrate distillation, solid matter is obtained；
By solid matter washing, filter and dry, obtain 3- amino-4-fluorophenols.
The present invention uses the conventional filter method in this area to the no particular/special requirement of filtering.
In the present invention, the distillation is preferably air-distillation, is steamed the organic solvent in the filtrate by distilling,
Obtain solid matter；The present invention does not have particular/special requirement to the actual temp for distilling, in a particular embodiment of the present invention, can be with root
The organic solvent species used during according to reaction determines vapo(u)rizing temperature.
It is 6.8~7.2, more preferably 6.9~7.1 that solid matter is preferably washed to water lotion pH value by the present invention.
In the present invention, the dry temperature is preferably 70~80 DEG C, more preferably 75~78 DEG C；The present invention is to drying
The specific time there is no particular/special requirement, by product drying to constant weight.
In some embodiments of the invention, after the completion of reaction, reaction solution can be cooled to room temperature with reactor,
Then nitrogen displacement remaining hydrogen therein is used, is replaced 3~5 times, make the hydrogen emptying in kettle, then driven kettle and take reaction solution
Go out to carry out the separation of product.
The fluoro- 5- nitrobenzene oxygen Ethyl formates of the bromo- 4- of 2- only can be synthesized 3- amino -4- fluorine by the present invention by single step reaction
Phenol, reaction equation is as shown in Equation 2：
The preparation method synthetic route that the present invention is provided is short, and step is few, and the three wastes that course of reaction is produced are few, to environment friend
Good, reaction condition is gentle, and synthetic product is without further purifying, it is only necessary to simple separation, and the product purity for obtaining is high,
High income, is adapted to industrialized production.
The preparation method of the 3- amino-4-fluorophenols provided the present invention with reference to embodiment is described in detail,
But they can not be interpreted as limiting the scope of the present invention.
Embodiment 1
To the addition 2- fluoro- 5- nitrobenzene oxygen Ethyl formate 183g (0.59mol) of bromo- 4-, absolute ethyl alcohol in 2L autoclaves
916g, palladium carbon 5g and potassium carbonate 244.3g (1.77mol), kettle is sealed after adding, and starts stirring, nitrogen displacement three times, and logical hydrogen is extremely
Pressure is 1.0MPa in kettle, is warming up to 45 DEG C and is reacted, and works as Hydrogen Vapor Pressure<During 0.5MPa, hydrogen to pressure 1.0MPa is mended, instead
Multiple operation is cooled to room temperature to pressure is not fallen after the completion of reaction, reacting liquid filtering is removed into catalyst after nitrogen displacement three times,
Filtrate air-distillation obtains solid crude product after steaming methyl alcohol, by 100g washings, filtering, then obtains light after 70 DEG C of vacuum drying
Yellow solid 3- amino-4-fluorophenols 68.3g；
Product structure is identified using nuclear magnetic resonance, gained appraising datum is as follows：1H NMR(DMSO-d6,
400MHz)δ8.857(s,1H),6.509-6.761(t,1H),6.126-6.206(d,1H),5.871-5.901(s,1H),
It can be seen from appraising datum, products therefrom is 3- amino-4-fluorophenols to 4.948 (s, 2H) really；
Use GC chromatograms (chromatographic column is SPB-5 posts, and hydrogen flame detector, detector temperature is 250 DEG C) detection product purity
And calculated yield, it is 99.2% that can obtain product purity, and yield is 91%.136 DEG C/the 20mmHg of boiling point of product.
Embodiment 2
To the addition 2- fluoro- 5- nitrobenzene oxygen Ethyl formate 183g (0.59mol) of bromo- 4-, methyl alcohol 916g, thunder in 2L autoclaves
Buddhist nun's nickel 5g and 1,3- propane diamine 174.9g (2.36mol), kettle is sealed after adding, and starts stirring, and nitrogen displacement three times leads to hydrogen to kettle
Interior pressure is 1.5MPa, is warming up to 40 DEG C and starts reaction, works as Hydrogen Vapor Pressure<During 1.0MPa, hydrogen to pressure 1.5MPa is mended, repeatedly
Operation is cooled to room temperature to pressure is not fallen after the completion of reaction, reacting liquid filtering is removed into catalyst after nitrogen displacement three times, filters
Liquid air-distillation obtains solid crude product after steaming methyl alcohol, and solid crude product is washed by 100g, filtering, then after 70 DEG C of vacuum drying
Obtain faint yellow solid 3- amino-4-fluorophenols 68.3g；
Product structure is identified using nuclear magnetic resonance, qualification result is consistent with embodiment 1, it is known that product is 3- really
Amino-4-fluorophenol；
Use GC chromatograms (chromatographic column is SPB-5 posts, and hydrogen flame detector, detector temperature is 250 DEG C) detection product purity
And calculated yield, it is 99.2% that can obtain product purity, and yield is 89%.136 DEG C/the 20mmHg of boiling point of product.
Embodiment 3
To the addition 2- fluoro- 5- nitrobenzene oxygen Ethyl formate 183g (0.59mol) of bromo- 4-, methyl alcohol 916g, palladium in 2L autoclaves
Carbon 5g and propylamine 104.4g (1.77mol), kettle is sealed after adding, and starts stirring, and nitrogen displacement three times leads to hydrogen to pressure
2.0MPa, is warming up to 40 DEG C and starts reaction, works as Hydrogen Vapor Pressure<During 1.5MPa, hydrogen is mended to pressure 2.0MPa, operate repeatedly to not
Untill falling pressure, room temperature is cooled to after the completion of reaction, reacting liquid filtering is removed into catalyst after nitrogen displacement, filtrate air-distillation is steamed
Solid crude product is obtained after going out methyl alcohol, by solid crude product by 100g washings, filtering, then obtains faint yellow after 70 DEG C of vacuum drying
Solid 3- amino-4-fluorophenols 68.3g；
Product structure is identified using nuclear magnetic resonance, qualification result is consistent with embodiment 1, it is known that product is 3- really
Amino-4-fluorophenol；
Use GC chromatograms (chromatographic column is SPB-5 posts, and hydrogen flame detector, detector temperature is 250 DEG C) detection product purity
And calculated yield, it is 99.2% that can obtain product purity, and yield is 92%.136 DEG C/the 20mmHg of boiling point of product.
Embodiment 4
To the addition 2- fluoro- 5- nitrobenzene oxygen Ethyl formate 183g (0.59mol) of bromo- 4-, ethyl acetate in 2L autoclaves
916g, Raney's nickel 18.3g and ethylenediamine 177g (2.95mol), kettle is sealed after adding, and starts stirring, and nitrogen displacement three times leads to hydrogen
To pressure 2.0MPa, it is warming up to 50 DEG C and starts reaction, works as Hydrogen Vapor Pressure<During 1.5MPa, hydrogen is mended to pressure 2.0MPa, grasp repeatedly
Make to pressure is not fallen, room temperature is cooled to after the completion of reaction, reacting liquid filtering is removed into catalyst, filtrate normal pressure after nitrogen displacement
Solid crude product is obtained after steaming methyl alcohol, by solid crude product by 100g washings, filtering, is then obtained after 75 DEG C of vacuum drying
Faint yellow solid 3- amino-4-fluorophenols 68.5g；
Product structure is identified using nuclear magnetic resonance, qualification result is consistent with embodiment 1, it is known that product is 3- really
Amino-4-fluorophenol；
Use GC chromatograms (chromatographic column is SPB-5 posts, and hydrogen flame detector, detector temperature is 250 DEG C) detection product purity
And calculated yield, it is 99.1% that can obtain product purity, and yield is 91.3%.136 DEG C/the 20mmHg of boiling point of product.
Embodiment 5
To in 2L autoclaves add the 2- fluoro- 5- nitrobenzene oxygen Ethyl formate 183g (0.59mol) of bromo- 4-, toluene 1800g,
Raney's nickel 14.64g and sodium carbonate 250.16g (2.36mol), kettle is sealed after adding, and starts stirring, and nitrogen displacement three times leads to hydrogen
To pressure 1.0MPa, it is warming up to 50 DEG C and starts reaction, works as Hydrogen Vapor Pressure<During 0.5MPa, hydrogen is mended to pressure 1.0MPa, grasp repeatedly
Make to pressure is not fallen, room temperature is cooled to after the completion of reaction, reacting liquid filtering is removed into catalyst, filtrate normal pressure after nitrogen displacement
Solid crude product is obtained after steaming methyl alcohol, by solid crude product by 100g washings, filtering, is then obtained after 75 DEG C of vacuum drying
Faint yellow solid 3- amino-4-fluorophenols 68.0g；
Product structure is identified using nuclear magnetic resonance, qualification result is consistent with embodiment 1, it is known that product is 3- really
Amino-4-fluorophenol；
Use GC chromatograms (chromatographic column is SPB-5 posts, and hydrogen flame detector, detector temperature is 250 DEG C) detection product purity
And calculated yield, it is 99.3% that can obtain product purity, and yield is 90.3%.136 DEG C/the 20mmHg of boiling point of product.
As seen from the above embodiment, the preparation method synthetic route that the present invention is provided is short, and step is few, from the fluoro- 5- of the bromo- 4- of 2-
Nitrobenzene oxygen Ethyl formate synthesis 3- amino-4-fluorophenols only need single step reaction, and the three wastes that course of reaction is produced are few, easily enter
Row industrialized production, synthetic product is without further purifying, it is only necessary to which simple separation is the product that can obtain high-purity, and yield is
90% or so.
As seen from the above embodiment, the present invention the above be only the preferred embodiment of the present invention, it is noted that for
For those skilled in the art, under the premise without departing from the principles of the invention, can also make it is some improvement and
Retouching, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of 3- amino-4-fluorophenols, it is characterised in that comprise the following steps：
The fluoro- 5- nitrobenzene oxygen Ethyl formates of the bromo- 4- of 2-, alkaline matter, hydrogenation catalyst and organic solvent are mixed, is mixed
Thing；
Hydrogenation reaction is carried out to being passed through hydrogen in the mixture in confined conditions, obtains 3- amino-4-fluorophenols；It is described logical
The air in enclosed system is discharged before entering hydrogen.
2. preparation method according to claim 1, it is characterised in that the alkaline matter is inorganic base and/or organic amine.
3. preparation method according to claim 2, it is characterised in that the inorganic base is sodium carbonate, potassium carbonate, hydroxide
The mixture of one or more in sodium and potassium hydroxide.
4. preparation method according to claim 2, it is characterised in that the organic amine is ethamine, triethylamine, propylamine, 1,
The mixture of one or more in 3- propane diamine and butylamine.
5. preparation method according to claim 1, it is characterised in that the hydrogenation catalyst is palladium carbon and/or Raney's nickel.
6. preparation method according to claim 1, it is characterised in that the organic solvent is methyl alcohol, ethanol, ethyl acetate
With the mixture of one or more in toluene.
7. preparation method according to claim 1, it is characterised in that the temperature of the hydrogenation reaction is 30~60 DEG C；
The initial pressure of the hydrogenation reaction is 1.0~2.0MPa, and pressure drop adds hydrogen to initial pressure when being more than 0.5MPa, instead
Should be to hydrogen not be inhaled.
8. preparation method according to claim 1, it is characterised in that the fluoro- 5- nitrobenzene oxygen Ethyl formates of the bromo- 4- of 2-
It is 1 with the mol ratio of alkaline matter:3~6；The quality of the hydrogenation catalyst and the fluoro- 5- nitrobenzene oxygen Ethyl formates of the bromo- 4- of 2-
Than being 0.05~0.15:1.
9. the preparation method according to claim 1 or 8, it is characterised in that the organic solvent and the fluoro- 5- nitre of the bromo- 4- of 2-
The mass ratio of base benzene oxygen Ethyl formate is 4~10:1.
10. preparation method according to claim 1, it is characterised in that also separated including product after the hydrogenation reaction, institute
Product separation is stated to comprise the following steps：
Reacting liquid filtering is removed into hydrogenation catalyst, filtrate is obtained；
By filtrate distillation, solid matter is obtained；
By solid matter washing, filter and dry, obtain 3- amino-4-fluorophenols.
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| CN110590570A (en) * | 2019-10-10 | 2019-12-20 | 西安凯立新材料股份有限公司 | Method for preparing halogenated p-aminophenol by catalytic hydrogenation of non-para-halogenated nitrobenzene |
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