CN105566131A - Method for catalytic reduction of m-nitroacetophenone for preparation of m-aminoacetophenone - Google Patents
Method for catalytic reduction of m-nitroacetophenone for preparation of m-aminoacetophenone Download PDFInfo
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- CN105566131A CN105566131A CN201510980640.8A CN201510980640A CN105566131A CN 105566131 A CN105566131 A CN 105566131A CN 201510980640 A CN201510980640 A CN 201510980640A CN 105566131 A CN105566131 A CN 105566131A
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- nitroacetophenone
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Abstract
The present invention provides a method for catalytic reduction of m-nitroacetophenone for preparation of m-aminoacetophenone, according to the method, hydrogen is used as a reducing agent, bismuth-compound-supported Pt is used as a catalyst, and the m-nitroacetophenone is highly-selectively reduced into the m-aminoacetophenone by a batch-type one-step reaction. The method reaction temperature is 30-120 DEG C, the reaction time is 1-20 hours, and the hydrogen partial pressure is 0.05-2.0MPa. The catalyst system can be used for efficiently catalytic hydrogenation of the m-nitroacetophenone, the m-aminoacetophenone yield is high; the hydrogen is used as the reducing agent, a main by-product is water, the method is green and environmentally-friendly; reaction conditions are mild, hydrogenation process equipment requirements are low, operation is simple; product separation and purification are simple, and the number of reusing times of the catalyst is high.
Description
Technical field
The present invention relates to a kind of process for catalytic synthesis of fine chemicals, a kind of is specifically reductive agent with hydrogen, with the platinum of bismuth compound load for catalyzer, by intermittent liquid-phase catalysis selective hydrogenation reaction, m-nitroacetophenone high-selectivity reduction is become m-aminophenyl ethyl ketone.
Background technology
M-aminophenyl ethyl ketone is important medicine and organic intermediate, and its derived product has important use.Such as m-hydroxy acetophenone is the intermediate of synthesis adrenomimetic drug medicine, and m chloroacetophenone can be used for the medicines such as synthesis bronchiectasis special medicine, anti-purplish or white patches on the skin leprosy, and 3-acetamido methyl phenyl ketone is then the intermediate of synthesis sedative hypnotic indene.
M-nitroacetophenone is relatively inexpensive to be easy to get, and can prepare m-aminophenyl ethyl ketone by selective reduction.Traditional iron powder reducing method is with a long history, and technique is simple, technology maturation, but production process produces reluctant iron mud and the waste water containing arylamine in a large number, environmental pollution serious (Chinese patent CN102249884B, CN104402695A).Take hydrogen as reductive agent, prepared by catalysis selective reduction m-nitroacetophenone that the method product yield of m-aminophenyl ethyl ketone is high, purity is high and it is little to pollute, product separation is simple, compared with traditional iron powder reducing method, there is obvious technology and cost advantage.But nitro functions, phenyl ring, carbonyl all may be reduced in hydrogenation process in m-nitroacetophenone structure, the selective control difficulty of product is high.Such as conventional palladium-carbon catalyst can realize the hydrogenating reduction of nitro functions in m-nitroacetophenone, even if but carbonyl also can simultaneously generating portion hydrogenation at ambient temperature, obtain the by products such as 3-Aminophenethyl alcohol, and then add the cost of product separation purification.Realize the key that m-nitroacetophenone highly effective hydrogenation prepares m-aminophenyl ethyl ketone and be to develop the catalyst system with high reactivity and highly selective.The invention provides a kind of method by intermittent liquid-phase catalytic hydrogenation reaction, m-nitroacetophenone high-selectivity reduction being become m-aminophenyl ethyl ketone, there is important using value.
Summary of the invention
A kind of m-nitroacetophenone highly effective hydrogenation is the object of the present invention is to provide to prepare the method for m-aminophenyl ethyl ketone, this method is that reductive agent, m-aminophenyl ethyl ketone yield are high with hydrogen, reaction conditions is gentle, catalyst recycling number of times is high, product separation is simple, the whole reaction process three wastes are few, and cost is low.
Technical scheme of the present invention: a kind of catalytic reduction m-nitroacetophenone prepares the method for m-aminophenyl ethyl ketone, thering is provided a kind of is reductive agent with hydrogen, with the platinum of bismuth compound load for catalyzer, by intermittent liquid-phase catalytic hydrogenation reaction, m-nitroacetophenone high-selectivity reduction is become the method for m-aminophenyl ethyl ketone; Concrete steps are as follows:
In batch reactor, add m-nitroacetophenone and catalyzer, the mass ratio of catalyzer and m-nitroacetophenone is 0.02-0.2; Add solvent again, the consumption of solvent is the 50-2000wt% of m-nitroacetophenone; Then, first use air in nitrogen replacement batch reactor, use hydrogen exchange nitrogen again, finally being filled with hydrogen to hydrogen partial pressure is 0.01-1.0MPa, although improve the raising that hydrogen pressure is conducive to speed of reaction if continue, but easily cause the hydrogenation of phenyl ring and carbonyl, cause significantly increasing of by product (as 3-Aminophenethyl alcohol), the requirement of equipment and production safety is also significantly improved simultaneously; Be warming up to temperature of reaction in whipping process, temperature of reaction is 30-120 DEG C, and the reaction times is 1-20 hour; Hydrogen consumption in reaction process, pressure drop, hydrogen make-up to hydrogen partial pressure is 0.01-1.0MPa, and when hydrogen no longer consumes, m-nitroacetophenone is converted into m-aminophenyl ethyl ketone completely; After reaction terminates, adopt centrifuging to be separated with reaction solution by catalyzer, reaction solution evaporates solvent surplus products and is m-aminophenyl ethyl ketone after collecting; Raw material m-nitroacetophenone transformation efficiency is greater than 99%, and m-aminophenyl ethyl ketone selectivity is greater than 99%.Even if extend the hydrogenation reaction time again, also can not there is hydrogenation reaction in the carbonyl in m-aminophenyl ethyl ketone further.Therefore, the hydrogenation operation in present method is very simple with control.The catalyzer of Separation and Recovery drops into reactor again, carries out hydrogenation reaction after adding solvent and raw material, reusable more than 20 times in this way.
Described catalyzer comprises active ingredient and carrier, and active ingredient is Pt, and carrier is Bi
2o
3, Bi
2o
5, (BiO)
2cO
3in one or more mixing; The mass ratio of active ingredient and carrier is 0.001-0.05.
The preparation method of catalyzer adopts deposition-precipitation method, and typical production is: get H
2ptCl
6solution, regulates pH to 12 with NaOH, is designated as A liquid.Get the Bi of 2g
2o
3be scattered in deionized water, be designated as B liquid.A liquid is slowly dropped in B liquid, and Keep agitation 18h.Then, filter, wash to pH=7.Finally, dry, 200 DEG C of roastings.Gained catalyzer needs to use H before use
2reductase 12 h under 200 DEG C of conditions.
Reaction system solvent for use is one or two or more kinds mixing in methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, sec-butyl alcohol, isopropylcarbinol, the trimethyl carbinol, and in reaction system, the consumption of solvent is the 50-2000wt% of m-nitroacetophenone.Solvent increases, and speed of reaction declines, and causes cost to raise simultaneously; Solvent reduces, and m-nitroacetophenone and target product m-aminophenyl ethyl ketone can not dissolve completely, are unfavorable for the carrying out of hydrogenation reaction equally.
Beneficial effect of the present invention: catalyst system used can efficient catalytic hydrogenation m-nitroacetophenone, and m-aminophenyl ethyl ketone yield is high; Hydrogen is reductive agent, and by product is mainly water, environmental protection; Reaction conditions is gentle, and hydrogenation process is low for equipment requirements, simple to operate; It is high that product separation is purified simply, number of times applied mechanically by catalyzer.
Accompanying drawing explanation
Fig. 1 is raw material m-nitroacetophenone color atlas (chromatographic signal appears at 13.2min) of the present invention.
Fig. 2 is the present invention's hydrogenation reaction solution color atlas (12.3min is excessive hydrogenation product 3-Aminophenethyl alcohol signal, and 12.8min is target product 3-aminoacetophenone signal) on commercialization palladium-carbon catalyst.
Fig. 3 is the method hydrogenation reaction solution color atlas (12.8min is target product 3-aminoacetophenone signal) that the present invention uses this patent to provide.
Embodiment
Below in conjunction with accompanying drawing and technical scheme, further illustrate the specific embodiment of the present invention.
Embodiment 1
By 2.0g m-nitroacetophenone, 0.2gPt/Bi
2o
3(Pt content is 0.2wt%), 10mL anhydrous methanol adds in 50mL batch reactor, successively reacts gas reactor 3-5 time with nitrogen and hydrogen exchange, is filled with hydrogen to pressure 1.0MPa, be warming up to 70 DEG C under continuous stirring, stirring velocity is 600-800 rev/min.If total pressure drops to below 0.5MPa, then hydrogen make-up is to original pressure.After 4h, total pressure no longer changes, and stops stirring, cool to room temperature.Centrifugal to mixture after reaction, bottom is yellow catalyst, and supernatant liquor is green (if m-nitroacetophenone transforms not exclusively, then supernatant liquor is yellow-green colour, and by product has nitro moiety hydrogenation products nitroso compound).The supernatant liquor that takes a morsel adopts gas chromatographic analysis, and m-nitroacetophenone transformation efficiency is greater than 99.9%, and m-aminophenyl ethyl ketone selectivity is greater than 99.9% (Fig. 3).Removed in filtrate by rotary evaporation and obtain product m-aminophenyl ethyl ketone after methyl alcohol, separation yield 99%.
Palladium-carbon catalyst (the 1wt% of commodity in use, Sigma-Aldrich), time, under same reaction conditions, (catalyzer material rate, temperature of reaction, reaction times, hydrogen pressure, solvent load, stirring velocity) then has a large amount of by product m-aminophenyl ethanol to produce (Fig. 2).
Embodiment 2
By 2.0g m-nitroacetophenone, 0.2gPt/Bi
2o
5(Pt content is 0.2wt%), 10mL dehydrated alcohol adds in 50mL batch reactor, successively reacts gas reactor 3-5 time with nitrogen and hydrogen exchange, is filled with hydrogen to pressure 0.1MPa, be warming up to 40 DEG C under continuous stirring, stirring velocity is 600-800 rev/min.If total pressure declines, hydrogen make-up is to original pressure.After 10h, total pressure no longer changes, and stops stirring, cool to room temperature.The supernatant liquor that takes a morsel adopts gas chromatographic analysis, and m-nitroacetophenone transformation efficiency is greater than 99.9%, and m-aminophenyl ethyl ketone selectivity is greater than 99.9%.Removed in filtrate by rotary evaporation and obtain product m-aminophenyl ethyl ketone after methyl alcohol, separation yield 98%.
Embodiment 3
By the catalyzer reclaimed in embodiment 1,10mL anhydrous methanol adds in 50mL batch reactor, add 2.0g m-nitroacetophenone, priority nitrogen and hydrogen exchange react gas reactor 3-5 time, be filled with hydrogen to pressure 1.0MPa, be warming up to 70 DEG C under continuous stirring, stirring velocity is 600-800 rev/min.If total pressure declines, hydrogen make-up is to original pressure.After certain hour, (see table 1) total pressure no longer changes, and stops stirring, cool to room temperature.The supernatant liquor that takes a morsel adopts gas chromatographic analysis, and m-nitroacetophenone transformation efficiency is greater than 99.9%, and m-aminophenyl ethyl ketone selectivity is greater than 99.9%.According to the method described above, recycled catalyzer, concrete outcome sees the following form:
Can see from table, catalyzer is reused through 20 times, still has higher catalytic activity, illustrates that this catalyzer has satisfactory stability.
Embodiment 4
By 2.0g m-nitroacetophenone, 0.3gPt/Bi
2o
3(Pt content is 0.5wt%), 5mL Virahol adds in 50mL batch reactor, successively reacts gas reactor 3-5 time with nitrogen and hydrogen exchange, is filled with hydrogen to pressure 0.5MPa, is warming up to 100 DEG C under constantly stirring.If total pressure declines, hydrogen make-up is to original pressure.After 1h, total pressure no longer changes, and stops stirring, cool to room temperature.The supernatant liquor that takes a morsel adopts gas chromatographic analysis, and m-nitroacetophenone transformation efficiency is greater than 99.9%, m-aminophenyl ethyl ketone selectivity 99.4%.
Embodiment 5
By 2.0g m-nitroacetophenone, 0.2g (BiO)
2cO
3(Pt content is 0.2wt%), 20mL sec-butyl alcohol adds in 50mL batch reactor, successively reacts gas reactor 3-5 time with nitrogen and hydrogen exchange, is filled with hydrogen to pressure 1.0MPa, stirred at ambient temperature.If total pressure declines, hydrogen make-up is to original pressure.After 10h, total pressure no longer changes, and stops stirring, cool to room temperature.The supernatant liquor that takes a morsel adopts gas chromatographic analysis, and m-nitroacetophenone transformation efficiency is greater than 99.9%, and m-aminophenyl ethyl ketone selectivity is 99.8%.
Embodiment 6
By 20g m-nitroacetophenone, 1.0g (BiO)
2cO
3(Pt content is 0.5wt%), 100mL isopropylcarbinol adds in 500mL batch reactor, successively reacts gas reactor 3-5 time with nitrogen and hydrogen exchange, is filled with hydrogen to pressure 0.5MPa, be warming up to 100 DEG C under continuous stirring, wherein mechanical stirring speed is 600-800 rev/min.If total pressure declines, hydrogen make-up is to original pressure.After 10h, total pressure no longer changes, and stops stirring, cool to room temperature.The supernatant liquor that takes a morsel adopts gas chromatographic analysis, and m-nitroacetophenone transformation efficiency is greater than 99.9%, and m-aminophenyl ethyl ketone selectivity is 99.6%.
Embodiment 7
By 400g m-nitroacetophenone, 5.0gPt/Bi
2o
3(Pt content is 1.0wt%), the 1000mL trimethyl carbinol adds in 50mL batch reactor, successively reacts gas reactor 3-5 time with nitrogen and hydrogen exchange, is filled with hydrogen to pressure 1.0MPa, be warming up to 120 DEG C under continuous stirring, wherein mechanical stirring speed is about 1000 revs/min.If total pressure declines, hydrogen make-up is to original pressure.After 20h, total pressure no longer changes, and stops stirring, cool to room temperature.The supernatant liquor that takes a morsel adopts gas chromatographic analysis, and m-nitroacetophenone transformation efficiency is greater than 99.9%, and m-aminophenyl ethyl ketone selectivity is 99.8%.
Embodiment 8
By 200g m-nitroacetophenone, 10.0gPt/Bi
2o
5(Pt content is 0.5wt%), 1000mL propyl carbinol adds in 50mL batch reactor, successively reacts gas reactor 3-5 time with nitrogen and hydrogen exchange, is filled with hydrogen to pressure 1.0MPa, be warming up to 80 DEG C under continuous stirring, wherein mechanical stirring speed is about 1000 revs/min.If total pressure declines, hydrogen make-up is to original pressure.After 20h, total pressure no longer changes, and stops stirring, cool to room temperature.The supernatant liquor that takes a morsel adopts gas chromatographic analysis, and m-nitroacetophenone transformation efficiency is greater than 99.0%, and m-aminophenyl ethyl ketone selectivity is 99.5%.
For being familiar with person skilled in the art of the present invention in the technical scope that the present invention reports, change can being expected easily or replace, all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention is not limited only to above embodiment, should be as the criterion with the protection domain of claim.
Claims (2)
1. catalytic reduction m-nitroacetophenone prepares a method for m-aminophenyl ethyl ketone, it is characterized in that, step is as follows: in batch reactor, add m-nitroacetophenone and catalyzer, and the mass ratio of catalyzer and m-nitroacetophenone is 0.02-0.2; Add solvent again, the consumption of solvent is the 50-2000wt% of m-nitroacetophenone; Then first use air in nitrogen replacement batch reactor, then use hydrogen exchange nitrogen, being finally filled with hydrogen to hydrogen partial pressure is 0.01-1.0MPa; Be warming up to temperature of reaction in whipping process, temperature of reaction is 30-120 DEG C, and the reaction times is 1-20 hour; Hydrogen consumption in reaction process, pressure drop, hydrogen make-up to hydrogen partial pressure is 0.01-1.0MPa, and when hydrogen no longer consumes, m-nitroacetophenone is converted into m-aminophenyl ethyl ketone completely; After reaction terminates, adopt centrifuging to be separated with reaction solution by catalyzer, reaction solution evaporates solvent surplus products and is m-aminophenyl ethyl ketone after collecting;
Described catalyzer comprises active ingredient and carrier, and active ingredient is Pt, and carrier is Bi
2o
3, Bi
2o
5, (BiO)
2cO
3in one or more mixing; The mass ratio of active ingredient and carrier is 0.001-0.05.
2. method according to claim 1, is characterized in that, described solvent is one or more mixing in methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, sec-butyl alcohol, isopropylcarbinol, the trimethyl carbinol.
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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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|---|---|
| CN105566131A true CN105566131A (en) | 2016-05-11 |
| CN105566131B CN105566131B (en) | 2017-08-01 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110938008A (en) * | 2019-12-09 | 2020-03-31 | 南京杰运医药科技有限公司 | Preparation method of o-aminoacetophenone |
| CN111298816A (en) * | 2020-03-03 | 2020-06-19 | 苏州彼定新材料科技有限公司 | Preparation method of porous hydroxyapatite supported platinum catalyst |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104277020A (en) * | 2013-07-02 | 2015-01-14 | 中国科学院大连化学物理研究所 | Method for preparing 2, 5-furan diformic acid by water phase catalysis of 5-hydroxymethylfurfural |
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2015
- 2015-12-23 CN CN201510980640.8A patent/CN105566131B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104277020A (en) * | 2013-07-02 | 2015-01-14 | 中国科学院大连化学物理研究所 | Method for preparing 2, 5-furan diformic acid by water phase catalysis of 5-hydroxymethylfurfural |
Non-Patent Citations (2)
| Title |
|---|
| MAJID I. ABDUL-WAHAB ET AL.: "Hydrogenation of 3-nitroacetophenone over rhodium/silica catalysts:Effect of metal dispersion and catalyst support", 《APPLIED CATALYSIS A: GENERAL》 * |
| YINGCHUN YIN ET AL.: "Well-dispersed Pt on TiO2: A highly active and selective catalyst for hydrogenation of 3-nitroacetophenone", 《APPLIED CATALYSIS A: GENERAL》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110938008A (en) * | 2019-12-09 | 2020-03-31 | 南京杰运医药科技有限公司 | Preparation method of o-aminoacetophenone |
| CN111298816A (en) * | 2020-03-03 | 2020-06-19 | 苏州彼定新材料科技有限公司 | Preparation method of porous hydroxyapatite supported platinum catalyst |
| CN111298816B (en) * | 2020-03-03 | 2023-05-16 | 苏州彼定新材料科技有限公司 | Preparation method of porous hydroxyapatite supported platinum catalyst |
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