CN101544594A - A green catalyzed method for preparing 3-amino-9-ethyl carbazole - Google Patents
A green catalyzed method for preparing 3-amino-9-ethyl carbazole Download PDFInfo
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- CN101544594A CN101544594A CN200910136705A CN200910136705A CN101544594A CN 101544594 A CN101544594 A CN 101544594A CN 200910136705 A CN200910136705 A CN 200910136705A CN 200910136705 A CN200910136705 A CN 200910136705A CN 101544594 A CN101544594 A CN 101544594A
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Abstract
A green catalyzed method for preparing 3-amino-9-ethyl carbazole relates to production for 3-amino-9-ethyl carbazole. In the solvent, using 3-nitro-9-ethyl carbazole as material, heating and dissolving, using Ni/meso-porous carbon as catalyst, replacing air with nitrogen gas at least three times, replacing nitrogen with hydrogen at least three times, filling with hydrogen gas for catalyzed hydrogenation for preparing 3-amino-9-ethyl carbazole under reaction pressure 1.5-2.5 Mpa, reaction temperature 80-180 DEG C. The green catalyzed method for preparing 3-amino-9-ethyl carbazole of the invention adopts Ni/meso-porous carbon as catalyst for preparing 3-amino-9-ethyl carbazole from 3-nitro-9-ethyl carbazole, which can reduce waste of all kinds, energy consumption and cost, improve product yield; and product is easily separated.
Description
Technical field
The present invention relates to the preparation of 3-amino-9-ethyl carbazole, a kind of specifically green catalyzed method for preparing 3-amino-9-ethyl carbazole.
Background technology
3-amino-9-ethyl carbazole is the important intermediate of high-grade pigment permanent violet RL (C.I.PV23).Domestic production enterprise adopts the method for sodium sulfide reducing 3-nitro-9-ethyl carbazole to produce 3-amino-9-ethyl carbazole.For example Xie Qiusheng has reported (dyestuff and dyeing, 2003 (8): VOL40 (4): 198-200) prepare 3-amino-9-ethyl carbazole with sodium sulphite reduction 3-nitro-9-ethyl carbazole.For example to disclose when preparing permanent violet the method for reduction 3-nitro-9-ethyl carbazole also be to adopt the sodium sulphite reduction to CN:1916081A, and the sodium sulfide reducing method need consume a large amount of Sodium Sulphide and ethanol, the energy consumption height, and yield is lower, causes production cost higher; Particularly produce a large amount of alkaline sulfur-containing waste waters, if serious without administering the discharging environmental pollution.Also there is the Raney-Ni of employing to prepare 3-amino-9-ethyl carbazole as catalyst to catalyzing hydrogenating 3-nitro-9-ethyl carbazole, for example permitted painting and reported (dyestuff and dyeing, 2003 (10): VOL40 (5): be that catalyst to catalyzing hydrogenating prepares 3-amino-9-ethyl carbazole 281-282) with modification Raney-Ni.The external general precious metal catalyst hydrogenation that adopts, as big Japanese ink and Bayer all with rare precious metals catalyst 3-nitro-9-ethyl carbazole hydrogenation preparing 3-amino-9-ethyl carbazole, but this method catalyzer cost costliness.
Summary of the invention
At the defective that exists in the prior art, the object of the present invention is to provide the method for a kind of green catalyzed 3-of preparation amino-9-ethyl carbazole, adopt the Ni/ mesoporous carbon to prepare 3-amino-9-ethyl carbazole as catalyst 3-nitro-9-ethyl carbazole, can reduce the three wastes, and product is easily separated, help improving reaction yield, cut down the consumption of energy and cost.
For reaching above purpose, the technical scheme that the present invention takes is:
A kind of green catalyzed method for preparing 3-amino-9-ethyl carbazole, it is characterized in that: in solvent, with 3-nitro-9-ethyl carbazole is raw material, be catalyzer with the Ni/ mesoporous carbon again after the heating for dissolving, behind nitrogen replacement air at least 3 times, using hydrogen exchange nitrogen at least 3 times again, and then charge into hydrogen, is that 1.5～2.5MPa, temperature of reaction are to carry out catalytic hydrogenation reaction under 80～180 ℃ the reaction conditions to prepare 3-amino-9-ethyl carbazole in reaction pressure.
On the basis of technique scheme, described solvent is a kind of in orthodichlorobenzene, hexahydroaniline, the Virahol, and the consumption of solvent is 3～9mL/g3-nitro-9-ethyl carbazole.
On the basis of technique scheme, the content of Ni is 20% of whole catalyst quality in mass in the described Ni/ gold/mesoporous carbon catalyst; The consumption of Ni/ gold/mesoporous carbon catalyst is 2～10% of 3-nitro-9-ethyl carbazole quality in mass.
The green catalyzed method for preparing 3-amino-9-ethyl carbazole of the present invention, adopt the Ni/ mesoporous carbon to prepare 3-amino-9-ethyl carbazole, can reduce the three wastes, and product is easily separated as catalyst 3-nitro-9-ethyl carbazole, help improving reaction yield, cut down the consumption of energy and cost.
Embodiment
The invention discloses the method for a kind of green catalyzed 3-of preparation amino-9-ethyl carbazole, in solvent, with 3-nitro-9-ethyl carbazole is raw material, be catalyzer with the Ni/ mesoporous carbon again after the heating for dissolving, behind nitrogen replacement air at least 3 times, using hydrogen exchange nitrogen at least 3 times again, and then charge into hydrogen, is that 1.5～2.5MPa, temperature of reaction are to carry out catalytic hydrogenation reaction under 80～180 ℃ the reaction conditions to prepare 3-amino-9-ethyl carbazole in reaction pressure.For example: said reaction pressure can be 1.5MPa, 1.6MPa, 1.7MPa, 1.8MPa, 1.9MPa, 2MPa, 2.1MPa, 2.2MPa, 2.3MPa, 2.4MPa or 2.5MPa; Said temperature of reaction can be 80 ℃, 82 ℃, 84 ℃, 86 ℃, 88 ℃, 90 ℃, 92 ℃, 94 ℃, 96 ℃, 98 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, 155 ℃, 160 ℃, 165 ℃, 170 ℃, 175 ℃ or 180 ℃.
On the basis of technique scheme, described solvent is a kind of in orthodichlorobenzene, hexahydroaniline, the Virahol, and the consumption of solvent is 3～9mL/g 3-nitro-9-ethyl carbazole.For example: the consumption of said solvent is 3mL/g, 3.5mL/g, 4mL/g, 4.5mL/g, 5mL/g, 5.5mL/g, 6mL/g, 6.5mL/g, 7mL/g, 7.5mL/g, 8mL/g, 8.5mL/g or 9mL/g 3-nitro-9-ethyl carbazole.
On the basis of technique scheme, the content of Ni is 20% of whole catalyst quality in mass in the described Ni/ gold/mesoporous carbon catalyst; The consumption of Ni/ gold/mesoporous carbon catalyst is 2～10% of 3-nitro-9-ethyl carbazole quality in mass.For example: the consumption of Ni/ mesoporous carbon is 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%.
Further specify method of the present invention below in conjunction with specific embodiment:
Embodiment 1:
In the beaker of 500mL, add 35g 3-nitro-9-ethyl carbazole and 280mL Virahol, drop into after the heating for dissolving in the autoclave of 0.5L, then, add 3.5g Ni/ mesoporous carbon, fasten valve.With nitrogen replacement 3～5 times, use hydrogen exchange again 3 times, feed hydrogen to 1MPa, be warming up to 180 ℃, hydrogen make-up is to 2.5MPa, and reaction is to not inhaling till the hydrogen.Cool to 60 ℃, leave standstill discharging after 1 hour, filter the back and use liquid-phase chromatographic analysis, 3-nitro-9-ethyl carbazole transformation efficiency is 97%, and yield is 87%.
Embodiment 2:
In the beaker of 500mL, add 35g (pure meter) 3-nitro-9-ethyl carbazole and 280mL Virahol, drop into after the heating for dissolving in the autoclave of 0.5L, then, add 3.5g Ni/ mesoporous carbon, fasten valve.With nitrogen replacement 3～5 times, use hydrogen exchange again 3 times, feed hydrogen to 1MPa, be warming up to 100 ℃, hydrogen make-up is to 2.5MPa, and reaction is to not inhaling till the hydrogen.Cool to 60 ℃, leave standstill discharging after 1 hour, filter the back and use liquid-phase chromatographic analysis, 3-nitro-9-ethyl carbazole transformation efficiency is 95%, and yield is 92%.
Embodiment 3:
In the beaker of 500mL, add 35g (pure meter) 3-nitro-9-ethyl carbazole and 315mL orthodichlorobenzene, drop into after the heating for dissolving in the autoclave of 0.5L, then, add 0.7g Ni/ mesoporous carbon, fasten valve.With nitrogen replacement 3～5 times, use hydrogen exchange again 3 times, feed hydrogen to 1MPa, be warming up to 160 ℃, hydrogen make-up is to 2MPa, and reaction is to not inhaling till the hydrogen.Cool to 60 ℃, leave standstill discharging after 1 hour, filter the back and use liquid-phase chromatographic analysis, 3-nitro-9-ethyl carbazole transformation efficiency is 98%, and yield is 96%.
Embodiment 4:
In the beaker of 500mL, add 35g (pure meter) 3-nitro-9-ethyl carbazole and 105mL hexahydroaniline, drop into after the heating for dissolving in the autoclave of 0.5L, then, add 3g Ni/ mesoporous carbon, fasten valve.With nitrogen replacement 3～5 times, use hydrogen exchange again 3 times, feed hydrogen to 1MPa, be warming up to 130 ℃, reaction is to not inhaling till the hydrogen.Hydrogen make-up cools to 60 ℃ to 2MPa, leaves standstill discharging after 1 hour, filters the back and uses liquid-phase chromatographic analysis, and 3-nitro-9-ethyl carbazole transformation efficiency is 93%, and yield is 90%.
Embodiment 5:
In the beaker of 500mL, add 35g (pure meter) 3-nitro-9-ethyl carbazole and 210mL hexahydroaniline, drop into after the heating for dissolving in the autoclave of 0.5L, then, add 1.75g Ni/ mesoporous carbon, fasten valve.With nitrogen replacement 3～5 times, use hydrogen exchange again 3 times, feed hydrogen to 0.5MPa, be warming up to 130 ℃, hydrogen make-up is to 1.5MPa, and reaction is to not inhaling till the hydrogen.Cool to 60 ℃, leave standstill discharging after 1 hour, filter the back and use liquid-phase chromatographic analysis, 3-nitro-9-ethyl carbazole transformation efficiency is 97%, and yield is 95%.
By above-mentioned specific embodiment as seen, reaction is finished after-filtration and can be obtained 3-amino-9-ethyl carbazole, and product is easily separated.
Claims (3)
1. green catalyzed method for preparing 3-amino-9-ethyl carbazole, it is characterized in that: in solvent, with 3-nitro-9-ethyl carbazole is raw material, be catalyzer with the Ni/ mesoporous carbon again after the heating for dissolving, behind nitrogen replacement air at least 3 times, using hydrogen exchange nitrogen at least 3 times again, and then charge into hydrogen, is that 1.5～2.5MPa, temperature of reaction are to carry out catalytic hydrogenation reaction under 80～180 ℃ the reaction conditions to prepare 3-amino-9-ethyl carbazole in reaction pressure.
2. the green catalyzed method for preparing 3-amino-9-ethyl carbazole as claimed in claim 1 is characterized in that: described solvent is a kind of in orthodichlorobenzene, hexahydroaniline, the Virahol, and the consumption of solvent is 3～9mL/g3-nitro-9-ethyl carbazole.
3. the green catalyzed method for preparing 3-amino-9-ethyl carbazole as claimed in claim 1 is characterized in that: the content of Ni is 20% of whole catalyst quality in mass in the described Ni/ gold/mesoporous carbon catalyst; The consumption of Ni/ gold/mesoporous carbon catalyst is 2～10% of 3-nitro-9-ethyl carbazole quality in mass.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101817990A (en) * | 2010-05-04 | 2010-09-01 | 江西紫晶化学有限公司 | Method for synthesizing permanent violet |
| CN106831537A (en) * | 2017-02-20 | 2017-06-13 | 东台市新锦泰化工有限公司 | Permanent violet RL intermediate condensate synthesis techniques |
| CN107935916A (en) * | 2017-10-27 | 2018-04-20 | 江苏仁欣化工股份有限公司 | The method that catalytic hydrogenation produces permanent violet intermediate |
| CN111013593A (en) * | 2020-01-06 | 2020-04-17 | 苏州明德新能源技术有限公司 | In-situ prepared nickel-based catalyst for catalyzing hydrogen absorption and hydrogen desorption of liquid organic hydrogen carrier and preparation method thereof |
-
2009
- 2009-05-13 CN CN200910136705A patent/CN101544594A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101817990A (en) * | 2010-05-04 | 2010-09-01 | 江西紫晶化学有限公司 | Method for synthesizing permanent violet |
| CN101817990B (en) * | 2010-05-04 | 2012-10-17 | 江西海天药业有限公司 | Method for synthesizing permanent violet |
| CN106831537A (en) * | 2017-02-20 | 2017-06-13 | 东台市新锦泰化工有限公司 | Permanent violet RL intermediate condensate synthesis techniques |
| CN106831537B (en) * | 2017-02-20 | 2019-12-06 | 东台市新锦泰化工有限公司 | Process for synthesizing permanent violet RL intermediate condensate |
| CN107935916A (en) * | 2017-10-27 | 2018-04-20 | 江苏仁欣化工股份有限公司 | The method that catalytic hydrogenation produces permanent violet intermediate |
| CN111013593A (en) * | 2020-01-06 | 2020-04-17 | 苏州明德新能源技术有限公司 | In-situ prepared nickel-based catalyst for catalyzing hydrogen absorption and hydrogen desorption of liquid organic hydrogen carrier and preparation method thereof |
| CN111013593B (en) * | 2020-01-06 | 2022-06-10 | 苏州明德新能源技术有限公司 | In-situ prepared nickel-based catalyst for catalyzing hydrogen absorption and desorption of liquid organic hydrogen carrier and preparation method thereof |
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Open date: 20090930 |