CN105566131B - It is a kind of to be catalyzed the method that reduction m-nitroacetophenone prepares m-aminophenyl ethyl ketone - Google Patents
It is a kind of to be catalyzed the method that reduction m-nitroacetophenone prepares m-aminophenyl ethyl ketone Download PDFInfo
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- CN105566131B CN105566131B CN201510980640.8A CN201510980640A CN105566131B CN 105566131 B CN105566131 B CN 105566131B CN 201510980640 A CN201510980640 A CN 201510980640A CN 105566131 B CN105566131 B CN 105566131B
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- nitroacetophenone
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Abstract
The method that reduction m-nitroacetophenone prepares m-aminophenyl ethyl ketone is catalyzed the invention provides a kind of, this method is using hydrogen as reducing agent, the Pt loaded using bismuth compound is catalyst, and batch (-type) single step reaction is by m-nitroacetophenone high-selectivity reduction into m-aminophenyl ethyl ketone.This method reaction temperature is 30 120 DEG C, and the reaction time is 1 20 hours, the 2.0MPa of hydrogen partial pressure 0.05.Catalyst system and catalyzing used being capable of efficient catalytic hydrogenation m-nitroacetophenone, m-aminophenyl ethyl ketone high income；Hydrogen is reducing agent, and accessory substance is mainly water, environmental protection；Reaction condition is gentle, and hydrogenation process is low for equipment requirements, simple to operate；It is high that product separating-purifying is simple, catalyst applies mechanically number of times.
Description
Technical field
It is specifically a kind of using hydrogen as reduction the present invention relates to a kind of process for catalytic synthesis of fine chemicals
Agent, the platinum loaded using bismuth compound is high by m-nitroacetophenone by intermittent liquid-phase catalysis selective hydrogenation reaction as catalyst
Selective reduction is into m-aminophenyl ethyl ketone.
Background technology
M-aminophenyl ethyl ketone is important medicine and organic intermediate, and product has important use downstream.Hydroxyl between for example
Benzoylformaldoxime is the intermediate for synthesizing adrenomimetic drug medicine, and m chloroacetophenone can be used for synthesis bronchiectasis special medicine, resist
The medicines such as purplish or white patches on the skin leprosy, 3- acetamidos acetophenone is then the intermediate for synthesizing hypnotic sedative agent indene.
M-nitroacetophenone is relatively inexpensive to be easy to get, and m-aminophenyl ethyl ketone can be prepared by selective reduction.Traditional iron powder
Reducing process is with a long history, and technique is simple, technology maturation, but production process produce a large amount of reluctant iron cements containing arylamine and
Waste water, environmental pollution is serious (Chinese patent CN102249884B, CN104402695A).Using hydrogen as reducing agent, pass through catalysis
Method product yield that selective reduction m-nitroacetophenone prepares m-aminophenyl ethyl ketone is high, purity is high and it is small to pollute, product separation
Simply, compared with traditional iron powder reducing method, with obvious technology and cost advantage.But nitro in m-nitroacetophenone structure
Functional group, phenyl ring, carbonyl may be reduced in hydrogenation process, and the selectivity control difficulty of product is high.Such as conventional palladium carbon
Catalyst can realize the hydrogenating reduction of nitro functions in m-nitroacetophenone, but also can even if carbonyl at ambient temperature
Partial hydrogenation occurs simultaneously, the accessory substances such as 3- Aminophenethyl alcohols are obtained, and then add the cost of product separating-purifying.Between realization
The key that nitro-acetophenone highly effective hydrogenation prepares m-aminophenyl ethyl ketone is to develop the catalysis with high activity and high selectivity
System.The present invention provide it is a kind of by intermittent liquid-phase catalytic hydrogenation reaction by m-nitroacetophenone high-selectivity reduction into an ammonia
The method of benzoylformaldoxime, with important application value.
The content of the invention
It is an object of the invention to provide a kind of method that m-nitroacetophenone highly effective hydrogenation prepares m-aminophenyl ethyl ketone, this
The method of kind is by reducing agent of hydrogen, m-aminophenyl ethyl ketone high income, and reaction condition is gentle, and catalyst recycling number of times is high, production
Product separation is simple, and the whole course of reaction three wastes are few, and cost is low.
Technical scheme：It is a kind of be catalyzed reduction m-nitroacetophenone prepare the method for m-aminophenyl ethyl ketone there is provided
The platinum that one kind is loaded using hydrogen as reducing agent, using bismuth compound as catalyst, by intermittent liquid-phase catalytic hydrogenation reaction will between
Method of the nitro-acetophenone high-selectivity reduction into m-aminophenyl ethyl ketone；Comprise the following steps that：
The mass ratio of m-nitroacetophenone and catalyst, catalyst and m-nitroacetophenone is added into batch reactor
For 0.02-0.2；Solvent is added, the consumption of solvent is the 50-2000wt% of m-nitroacetophenone；Then, nitrogen displacement is first used
Air in batch reactor, then nitrogen is replaced with hydrogen, it is 0.01-1.0MPa to be finally filled with hydrogen to hydrogen partial pressure, if after
Although the continuous Hydrogen Vapor Pressure that improves is conducive to the raising of reaction rate, but easily causes the hydrogenation of phenyl ring and carbonyl, causes accessory substance
(such as 3- Aminophenethyl alcohols) significantly increases, while the requirement to equipment and production safety is also greatly improved；Risen in whipping process
Temperature is to reaction temperature, and reaction temperature is 30-120 DEG C, and the reaction time is 1-20 hours；Under hydrogen consumption in course of reaction, pressure
Drop, hydrogen make-up to hydrogen partial pressure is 0.01-1.0MPa, and when hydrogen is no longer consumed, m-nitroacetophenone is fully converted to an ammonia
Benzoylformaldoxime；After reaction terminates, catalyst and reaction solution are separated using centrifugal process, after reaction solution is collected, solvent is evaporated remaining
Product is m-aminophenyl ethyl ketone；Raw material m-nitroacetophenone conversion ratio is more than 99%, and m-aminophenyl ethyl ketone is selectively more than
99%.Even if extending the hydrogenation reaction time again, hydrogenation reaction also will not further occur for the carbonyl in m-aminophenyl ethyl ketone.Cause
This, the hydrogenation operation and control in this method are very simple.The catalyst of separation and recovery puts into reactor again, adds molten
Hydrogenation reaction is carried out after agent and raw material, reusable more than 20 times in this way.
Described catalyst includes active component and carrier, and active component is Pt, and carrier is Bi2O3、Bi2O5、(BiO)2CO3
One or both of it is mixed above；The mass ratio of active component and carrier is 0.001-0.05.
The preparation method of catalyst uses deposition-precipitation method, and typical production is：Take H2PtCl6Solution, is adjusted with NaOH
PH is designated as A liquid to 12.Take 2g Bi2O3It is scattered in deionized water, is designated as B liquid.A liquid is slowly added dropwise into B liquid, and continued
Stir 18h.Then, filter, wash to pH=7.Finally, dry, 200 DEG C of roastings.Gained catalyst is using preceding needing to use H2
Reductase 12 h under the conditions of 200 DEG C.
Reaction system solvent for use is methanol, ethanol, normal propyl alcohol, isopropanol, n-butanol, sec-butyl alcohol, isobutanol, the tert-butyl alcohol
In one or two or more kinds of mixing, the consumption of solvent is the 50-2000wt% of m-nitroacetophenone in reaction system.Solvent increases
Many, reaction rate declines, while causing cost to raise；Solvent is reduced, m-nitroacetophenone and target product m-aminophenyl ethyl ketone
It can not be completely dissolved, equally be unfavorable for the progress of hydrogenation reaction.
Beneficial effects of the present invention：Catalyst system and catalyzing used being capable of efficient catalytic hydrogenation m-nitroacetophenone, m-aminophenyl second
Ketone high income；Hydrogen is reducing agent, and accessory substance is mainly water, environmental protection；Reaction condition is gentle, and hydrogenation process is to equipment requirement
It is low, simple to operate；It is high that product separating-purifying is simple, catalyst applies mechanically number of times.
Brief description of the drawings
Fig. 1 is the raw material m-nitroacetophenone chromatogram of the present invention (chromatographic signal appears in 13.2min).
Fig. 2 is that (12.3min is excessive hydrogenation product to the hydrogenation reaction solution chromatogram of the invention on commercialization palladium-carbon catalyst
3- Aminophenethyl alcohol signals, 12.8min is target product 3- aminoacetophenones signal).
Fig. 3 is that (12.8min is target product 3- ammonia to the method hydrogenation reaction solution chromatogram of the invention using this patent offer
Benzoylformaldoxime signal).
Embodiment
Below in conjunction with accompanying drawing and technical scheme, the embodiment of the present invention is further illustrated.
Embodiment 1
By 2.0g m-nitroacetophenones, 0.2g Pt/Bi2O3(Pt contents are 0.2wt%), 10mL absolute methanols add 50mL
In batch reactor, successively with gas in nitrogen and hydrogen replacement reaction kettle 3-5 times, hydrogen is filled with to pressure 1.0MPa, no
70 DEG C are warming up under disconnected stirring, mixing speed is 600-800 revs/min.If gross pressure drops to below 0.5MPa, supplement
Hydrogen is to initial pressure.Gross pressure no longer changes after 4h, stops stirring, is cooled to room temperature.Mixture after reaction is centrifuged, bottom
For yellow catalyst, for green, (if m-nitroacetophenone conversion is incomplete, supernatant is yellow green, accessory substance to supernatant
There is nitro moiety hydrogenation products nitroso compound).A small amount of supernatant is taken to use gas chromatographic analysis, m-nitroacetophenone conversion
Rate is more than 99.9%, and m-aminophenyl ethyl ketone is selectively more than 99.9% (Fig. 3).Removed by rotary evaporation in filtrate and obtained after methanol
Product m-aminophenyl ethyl ketone, separation yield 99%.
During palladium-carbon catalyst (1wt%, the Sigma-Aldrich) of commodity in use, (catalysagen under same reaction conditions
Material ratio, reaction temperature, reaction time, Hydrogen Vapor Pressure, solvent load, mixing speed) then there is substantial amounts of accessory substance m-aminophenyl
Ethanol produces (Fig. 2).
Embodiment 2
By 2.0g m-nitroacetophenones, 0.2g Pt/Bi2O5(Pt contents are 0.2wt%), 10mL absolute ethyl alcohols add 50mL
In batch reactor, successively with gas in nitrogen and hydrogen replacement reaction kettle 3-5 times, hydrogen is filled with to pressure 0.1MPa, no
40 DEG C are warming up under disconnected stirring, mixing speed is 600-800 revs/min.Hydrogen make-up is pressed to initial if gross pressure declines
Power.Gross pressure no longer changes after 10h, stops stirring, is cooled to room temperature.A small amount of supernatant is taken to use gas chromatographic analysis, a nitre
Benzoylformaldoxime conversion ratio is more than 99.9%, and m-aminophenyl ethyl ketone is selectively more than 99.9%.Removed by rotary evaporation in filtrate
Product m-aminophenyl ethyl ketone, separation yield 98% are obtained after methanol.
Embodiment 3
The catalyst that will be reclaimed in embodiment 1,10mL absolute methanols are added in 50mL batch reactors, are added between 2.0g
Nitro-acetophenone, successively with gas in nitrogen and hydrogen replacement reaction kettle 3-5 times, is filled with hydrogen to pressure 1.0MPa, constantly stirs
Mix down and be warming up to 70 DEG C, mixing speed is 600-800 revs/min.Hydrogen make-up is to initial pressure if gross pressure declines.One
(being shown in Table 1) after fixing time, gross pressure no longer changes, and stops stirring, is cooled to room temperature.A small amount of supernatant is taken using gas-chromatography point
Analysis, m-nitroacetophenone conversion ratio is more than 99.9%, and m-aminophenyl ethyl ketone is selectively more than 99.9%.According to the method described above, follow
Ring set catalyst, concrete outcome see the table below：
It can see from table, catalyst still has higher catalytic activity by 20 reuses, illustrate that the catalyst has
There is good stability.
Embodiment 4
By 2.0g m-nitroacetophenones, 0.3g Pt/Bi2O3(Pt contents are 0.5wt%), 5mL isopropanols are added between 50mL
In formula of having a rest reactor, successively with gas in nitrogen and hydrogen replacement reaction kettle 3-5 times, hydrogen is filled with to pressure 0.5MPa, constantly
100 DEG C are warming up under stirring.Hydrogen make-up is to initial pressure if gross pressure declines.Gross pressure no longer changes after 1h, stops
Stirring, is cooled to room temperature.A small amount of supernatant is taken to use gas chromatographic analysis, m-nitroacetophenone conversion ratio is more than 99.9%,
Aminoacetophenone selectivity 99.4%.
Embodiment 5
By 2.0g m-nitroacetophenones, 0.2g (BiO)2CO3(Pt contents are 0.2wt%), 20mL sec-butyl alcohols are added between 50mL
In formula of having a rest reactor, successively with gas in nitrogen and hydrogen replacement reaction kettle 3-5 times, hydrogen is filled with to pressure 1.0MPa, room temperature
Lower stirring.Hydrogen make-up is to initial pressure if gross pressure declines.Gross pressure no longer changes after 10h, stops stirring, is cooled to
Room temperature.A small amount of supernatant is taken to use gas chromatographic analysis, m-nitroacetophenone conversion ratio is more than 99.9%, the choosing of m-aminophenyl ethyl ketone
Selecting property is 99.8%.
Embodiment 6
By 20g m-nitroacetophenones, 1.0g (BiO)2CO3(Pt contents are 0.5wt%), 100mL isobutanols add 500mL
In batch reactor, successively with gas in nitrogen and hydrogen replacement reaction kettle 3-5 times, hydrogen is filled with to pressure 0.5MPa, no
100 DEG C are warming up under disconnected stirring, wherein mechanical agitation speed is 600-800 revs/min.The hydrogen make-up if gross pressure declines
To initial pressure.Gross pressure no longer changes after 10h, stops stirring, is cooled to room temperature.A small amount of supernatant is taken using gas-chromatography point
Analysis, m-nitroacetophenone conversion ratio is more than 99.9%, and m-aminophenyl ethyl ketone is selectively 99.6%.
Embodiment 7
By 400g m-nitroacetophenones, 5.0g Pt/Bi2O3(Pt contents are 1.0wt%), the 1000mL tert-butyl alcohols add 50mL
In batch reactor, successively with gas in nitrogen and hydrogen replacement reaction kettle 3-5 times, hydrogen is filled with to pressure 1.0MPa, no
120 DEG C are warming up under disconnected stirring, wherein mechanical agitation speed is about 1000 revs/min.The hydrogen make-up if gross pressure declines
To initial pressure.Gross pressure no longer changes after 20h, stops stirring, is cooled to room temperature.A small amount of supernatant is taken using gas-chromatography point
Analysis, m-nitroacetophenone conversion ratio is more than 99.9%, and m-aminophenyl ethyl ketone is selectively 99.8%.
Embodiment 8
By 200g m-nitroacetophenones, 10.0g Pt/Bi2O5(Pt contents are 0.5wt%), 1000mL n-butanols are added
In 50mL batch reactors, successively with gas in nitrogen and hydrogen replacement reaction kettle 3-5 times, hydrogen is filled with to pressure
1.0MPa, is stirred continuously down and is warming up to 80 DEG C, wherein mechanical agitation speed is about 1000 revs/min.If gross pressure declines
Hydrogen make-up is to initial pressure.Gross pressure no longer changes after 20h, stops stirring, is cooled to room temperature.A small amount of supernatant is taken to use gas
Analysis of hplc, m-nitroacetophenone conversion ratio is more than 99.0%, and m-aminophenyl ethyl ketone is selectively 99.5%.
For being familiar with person skilled in the art of the present invention in the technical scope that the present invention is reported, change can be readily occurred in
Change or replace, should all be included within the scope of the present invention.Therefore, protection scope of the present invention is not limited only to above implementation
Example, it should be defined by scope of the claims.
Claims (2)
1. a kind of be catalyzed the method that reduction m-nitroacetophenone prepares m-aminophenyl ethyl ketone, it is characterised in that step is as follows：Xiang Jian
Add m-nitroacetophenone and catalyst in formula of having a rest reactor, the mass ratio of catalyst and m-nitroacetophenone is 0.02-0.2；
Solvent is added, the consumption of solvent is the 50-2000wt% of m-nitroacetophenone；Then nitrogen displacement batch reactor is first used
Interior air, then nitrogen is replaced with hydrogen, it is 0.01-1.0MPa to be finally filled with hydrogen to hydrogen partial pressure；It is warming up in whipping process
Reaction temperature, reaction temperature is 30-120 DEG C, and the reaction time is 1-20 hours；Hydrogen consumption in course of reaction, pressure declines, and mends
It is 0.01-1.0MPa to be flushed with hydrogen gas to hydrogen partial pressure, and when hydrogen is no longer consumed, m-nitroacetophenone is fully converted to m-aminophenyl second
Ketone；After reaction terminates, catalyst and reaction solution are separated using centrifugal process, after reaction solution is collected, solvent surplus products are evaporated i.e.
For m-aminophenyl ethyl ketone；
Described catalyst includes active component and carrier, and active component is Pt, and carrier is Bi2O3、Bi2O5、(BiO)2CO3In
One or more mixing；The mass ratio of active component and carrier is 0.001-0.05.
2. according to the method described in claim 1, it is characterised in that described solvent be methanol, ethanol, normal propyl alcohol, isopropanol,
One or both of n-butanol, sec-butyl alcohol, isobutanol, the tert-butyl alcohol are mixed above.
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| CN201510980640.8A CN105566131B (en) | 2015-12-23 | 2015-12-23 | It is a kind of to be catalyzed the method that reduction m-nitroacetophenone prepares m-aminophenyl ethyl ketone |
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| CN201510980640.8A CN105566131B (en) | 2015-12-23 | 2015-12-23 | It is a kind of to be catalyzed the method that reduction m-nitroacetophenone prepares m-aminophenyl ethyl ketone |
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