CN102249984A - Preparation method of carbazole - Google Patents
Preparation method of carbazole Download PDFInfo
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- CN102249984A CN102249984A CN201110151504XA CN201110151504A CN102249984A CN 102249984 A CN102249984 A CN 102249984A CN 201110151504X A CN201110151504X A CN 201110151504XA CN 201110151504 A CN201110151504 A CN 201110151504A CN 102249984 A CN102249984 A CN 102249984A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention relates to a preparation method of carbazole, comprising the following steps of: adding an organic solvent, tetrahydrocarbazole and a catalyst to a reactor provided with a stirrer and a reflux condenser; firstly increasing temperature to remove low-boiling-point substances; continuously increasing the temperature to 140-300 DEG C to react till the transformation rate of the tetrahydrocarbazole is more than 99 percent so as to obtain reaction liquid; filtering the reaction liquid to recover the catalyst; distilling filter liquor to recover the organic solvent; and then carrying out cooling crystallization, filtering wash and drying to obtain the carbazole. The invention has the advantages of simple process, relatively moderate condition, high transformation rate and easiness in product separation and purification.
Description
Technical field
The present invention relates to a kind of preparation method of carbazole, belong to chemical field.
Background technology
Carbazole can be widely used in numerous areas such as dyestuff, pigment, plastics, medicine, photoelectric material as the important intermediate of fine chemicals, especially is used to make para-dye and high-grade pigment dyestuff, and the most representative is permanent violet RL.Up to the present, domestic used carbazole generally extracts from coal tar.In recent years,, the demand of carbazole is sharply increased to the research of carbazole and derivative thereof with use further deeply along with both at home and abroad, domestic carbazole disparities between supply and demand are more outstanding.Given this, to prepare carbazole imperative for chemical method.
Though the preparation method of the carbazole of having reported is a lot, have mostly that step is many, shortcomings such as severe reaction conditions, transformation efficiency are low, separation and purification difficulty, difficultly realize industrialization.U.S. Pat 2921942 provides a kind of pentanoic steam is fed to be equipped with in the high temperature reaction zone of supported palladium/platinum catalyst, dehydrocyclization prepares the method for carbazole, this method can realize continuous production, but complex process, the equipment requirements height, temperature of reaction height, optimum temps 450-570 ℃, transformation efficiency is less than 70%, and follows by products such as benzene, aniline, ammonia to produce in the process.For overcoming the shortcoming of gas-phase reaction, it is raw material with the pentanoic that U.S. Pat 5760247 has proposed a kind of, liquid phase reaction prepares the method for carbazole, this method is simple to operate, low for equipment requirements, temperature of reaction 220-310 ℃, but transformation efficiency less than 70% still, and, cause selectivity lower because the residence time is longer.It is dehydrogenating agent with the tetrachlorobenzoquinone that Mao Suchun etc. (synthesizing of carbazole come from 1996 the 7th phases " chemistry circular ", the 40-42 page or leaf) have proposed a kind of, and dehydrogenation prepares the method for carbazole to tetrahydro carbazole.This method temperature of reaction is low, and yield reaches as high as 95%, product purity 96.54%, but this method complex operation, owing to have a large amount of tetrachloro quinhydrones to generate, the separation and purification of products difficulty, and generation contains quinone waste water in a large number.
Summary of the invention
The preparation method who the purpose of this invention is to provide the carbazole that a kind of technology is simple, condition is gentle relatively, transformation efficiency is high, product purity is high.
For achieving the above object, the technical solution used in the present invention is:
A kind of preparation method of carbazole, it is characterized in that, may further comprise the steps: in the reactor of band stirring and reflux exchanger, add organic solvent, tetrahydro carbazole and catalyzer, heat up earlier and remove low-boiling-point substance, continue to be warming up to 140-220 ℃ and react, more than 99%, get reaction solution until the tetrahydro carbazole transformation efficiency, with reacting liquid filtering, reclaim catalyzer, organic solvent is reclaimed in the filtrate distillation, again through crystallisation by cooling, diafiltration, the dry carbazole that gets.
A kind of preparation method of carbazole, it is characterized in that, may further comprise the steps: in the reactor of band stirring and reflux exchanger, add tetrahydro carbazole, heat up after the fusing, add catalyzer, heating up then removes low-boiling-point substance, continuing to be warming up to 200-350 ℃ reacts, more than 99%, be cooled to 140-160 ℃ until the tetrahydro carbazole transformation efficiency, add organic solvent, after the heating for dissolving, get reaction solution,, reclaim catalyzer reacting liquid filtering, organic solvent is reclaimed in the filtrate distillation, again through crystallisation by cooling, diafiltration, the dry carbazole that gets.
Described organic solvent is dimethylbenzene, N, a kind of in dinethylformamide, N-Methyl pyrrolidone, orthodichlorobenzene, the trichlorobenzene, and the mass ratio of tetrahydro carbazole and organic solvent is 1:2-20.
Described catalyzer is a kind of in load platinum, supported palladium, the Lei Shi nickel, tetrahydro carbazole and give money as a gift after catalyst quality than being 10-1000:1.
Above-mentioned tetrahydro carbazole and give money as a gift after the catalyst quality ratio be preferably 50-200:1.
The load of described load platinum, supported palladium is a kind of in gac, mesoporous carbon, the aluminum oxide, and charge capacity is 0.5-20%.
Above-mentioned charge capacity is preferably 3-10%.
Advantage of the present invention: technology is simple, condition is gentle relatively, transformation efficiency is high, separation and purification of products is easy.
Embodiment
Following examples are intended to illustrate the present invention rather than to the bright further qualification of we.
Embodiment 1
In the flask of band stirring and reflux exchanger, adding 200g dimethylbenzene, 20g tetrahydro carbazole, 0.2g charge capacity are platinum/activated carbon catalyst (moisture 50%) of 3%, dehydration heats up earlier, continuing to be warming up to 140 ℃ reacts, until the tetrahydro carbazole transformation efficiency more than 99%, the reacting liquor while hot filtering recovering catalyst, dimethylbenzene is reclaimed in the filtrate distillation, again through crystallisation by cooling, diafiltration, dry 18.7g carbazole, the content 99.3% of getting.
Embodiment 2
In the flask of band stirring and reflux exchanger, add 40g N, dinethylformamide, 20g tetrahydro carbazole, 0.4g charge capacity are platinum/gold/mesoporous carbon catalyst (moisture 50%) of 6%, and the dehydration that heats up earlier continues to be warming up to 150 ℃ and reacts, until the tetrahydro carbazole transformation efficiency more than 99%, the reacting liquor while hot filtering recovering catalyst, N, dinethylformamide are reclaimed in the filtrate distillation, again through crystallisation by cooling, diafiltration, dry 18.4g carbazole, the content 99.8% of getting.
Embodiment 3
In the flask of band stirring and reflux exchanger, adding 100g N-Methyl pyrrolidone, 20g tetrahydro carbazole, 0.4g charge capacity are palladium/activated carbon catalyst (moisture 50%) of 10%, dehydration heats up earlier, continuing to be warming up to 200 ℃ reacts, until the tetrahydro carbazole transformation efficiency more than 99%, the reacting liquor while hot filtering recovering catalyst, N-Methyl pyrrolidone is reclaimed in the filtrate distillation, again through crystallisation by cooling, diafiltration, dry 18.4g carbazole, the content 98.7% of getting.
Embodiment 4
In the flask of band stirring and reflux exchanger, add 400g orthodichlorobenzene, 20g tetrahydro carbazole, 0.2g Lei Shi nickel (containing ethanol 50%), heat up earlier and take off ethanol, continuing to be warming up to 180 ℃ reacts, until the tetrahydro carbazole transformation efficiency more than 99%, the reacting liquor while hot filtering recovering catalyst, orthodichlorobenzene is reclaimed in the filtrate distillation, again through crystallisation by cooling, diafiltration, dry 17.1g carbazole, the content 98.8% of getting.
Embodiment 5
In the flask of band stirring and reflux exchanger, adding 300g trichlorobenzene, 20g tetrahydro carbazole, 0.1g charge capacity are platinum/aluminium oxide catalyst (moisture 50%) of 5%, dehydration heats up earlier, continuing to be warming up to 220 ℃ reacts, until the tetrahydro carbazole transformation efficiency more than 99%, the reacting liquor while hot filtering recovering catalyst, trichlorobenzene is reclaimed in the filtrate distillation, again through crystallisation by cooling, diafiltration, dry 18.6g carbazole, the content 99.1% of getting.
Embodiment 6
In the flask of band stirring and reflux exchanger, adding 300g trichlorobenzene, 20g tetrahydro carbazole, 0.16g charge capacity are palladium/gold/mesoporous carbon catalyst (moisture 50%) of 7%, dehydration heats up earlier, continuing to be warming up to 220 ℃ reacts, until the tetrahydro carbazole transformation efficiency more than 99%, the reacting liquor while hot filtering recovering catalyst, trichlorobenzene is reclaimed in the filtrate distillation, again through crystallisation by cooling, diafiltration, dry 19.1g carbazole, the content 99.7% of getting.
Embodiment 7
In the flask of band stirring and reflux exchanger, add the 200g tetrahydro carbazole, the fusing back adding 4g charge capacity that heats up is platinum/activated carbon catalyst (moisture 50%) of 10%, dehydration heats up earlier, continuing to be warming up to 200 ℃ gradually reacts, until the tetrahydro carbazole transformation efficiency more than 99%, be cooled to 150 ℃, add 500gN, dinethylformamide, after the heating for dissolving, the reacting liquor while hot filtering recovering catalyst, N, dinethylformamide are reclaimed in the filtrate distillation, again through crystallisation by cooling, diafiltration, dry 185.2g carbazole, the content 98.3% of getting.
Embodiment 8
In the flask of band stirring and reflux exchanger, add the 200g tetrahydro carbazole, the fusing back adding 1g charge capacity that heats up is palladium/gold/mesoporous carbon catalyst (moisture 50%) of 3%, dehydration heats up earlier, continuing to be warming up to 250 ℃ gradually reacts, until the tetrahydro carbazole transformation efficiency more than 99%, be cooled to 140 ℃, add 500gN, dinethylformamide, after the heating for dissolving, the reacting liquor while hot filtering recovering catalyst, N, dinethylformamide are reclaimed in the filtrate distillation, again through crystallisation by cooling, diafiltration, dry 184.6g carbazole, the content 98.3% of getting.
Embodiment 9
In the flask of band stirring and reflux exchanger, add the 200g tetrahydro carbazole, the fusing back adding 2g charge capacity that heats up is platinum/aluminium oxide catalyst (moisture 50%) of 6%, dehydration heats up earlier, continuing to be warming up to 300 ℃ gradually reacts, until the tetrahydro carbazole transformation efficiency more than 99%, be cooled to 150 ℃, add 500gN, dinethylformamide, after the heating for dissolving, the reacting liquor while hot filtering recovering catalyst, N, dinethylformamide are reclaimed in the filtrate distillation, again through crystallisation by cooling, diafiltration, dry 189.1g carbazole, the content 98.2% of getting.
Embodiment 10
In the flask of band stirring and reflux exchanger, add the 200g tetrahydro carbazole, fusing back adding 1.25g Lei Shi nickel (containing ethanol 50%) heats up, heat up earlier and take off ethanol, continuing to be warming up to 350 ℃ gradually reacts, until the tetrahydro carbazole transformation efficiency more than 99%, be cooled to 160 ℃, add 500gN, dinethylformamide, after the heating for dissolving, the reacting liquor while hot filtering recovering catalyst, N, dinethylformamide are reclaimed in the filtrate distillation, again through crystallisation by cooling, diafiltration, dry 185.9g carbazole, the content 98.8% of getting.
The present invention has that technology is simple, condition is gentle relatively, transformation efficiency is high, separation and purification of products is easy to advantage.
Claims (7)
1. the preparation method of a carbazole, it is characterized in that, may further comprise the steps: in the reactor of band stirring and reflux exchanger, add organic solvent, tetrahydro carbazole and catalyzer, heat up earlier and remove low-boiling-point substance, continue to be warming up to 140-220 ℃ and react, more than 99%, get reaction solution until the tetrahydro carbazole transformation efficiency, with reacting liquid filtering, reclaim catalyzer, organic solvent is reclaimed in the filtrate distillation, again through crystallisation by cooling, diafiltration, the dry carbazole that gets.
2. the preparation method of a carbazole, it is characterized in that, may further comprise the steps: in the reactor of band stirring and reflux exchanger, add tetrahydro carbazole, heat up after the fusing, add catalyzer, heating up then removes low-boiling-point substance, continuing to be warming up to 200-350 ℃ reacts, more than 99%, be cooled to 140-160 ℃ until the tetrahydro carbazole transformation efficiency, add organic solvent, after the heating for dissolving, get reaction solution,, reclaim catalyzer reacting liquid filtering, organic solvent is reclaimed in the filtrate distillation, again through crystallisation by cooling, diafiltration, the dry carbazole that gets.
3. the preparation method of a kind of carbazole according to claim 1 and 2, it is characterized in that: described organic solvent is dimethylbenzene, N, a kind of in dinethylformamide, N-Methyl pyrrolidone, orthodichlorobenzene, the trichlorobenzene, the mass ratio of tetrahydro carbazole and solvent is 1:2-20.
4. the preparation method of a kind of carbazole according to claim 1 and 2 is characterized in that: described catalyzer is a kind of in load platinum, supported palladium, the Lei Shi nickel, tetrahydro carbazole and give money as a gift after catalyst quality than being 10-1000:1.
5. the preparation method of a kind of carbazole according to claim 4 is characterized in that: described tetrahydro carbazole and give money as a gift after catalyst quality than being 50-200:1.
6. the preparation method of a kind of carbazole according to claim 4 is characterized in that: the load of described load platinum, supported palladium is a kind of in gac, mesoporous carbon, the aluminum oxide, and charge capacity is 0.5-20%.
7. the preparation method of a kind of carbazole according to claim 6, it is characterized in that: described charge capacity is 3%-10%.
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| CN201110151504XA CN102249984A (en) | 2011-06-08 | 2011-06-08 | Preparation method of carbazole |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103087550A (en) * | 2013-02-05 | 2013-05-08 | 马鞍山金镨新材料科技有限公司 | Permanent violet product synthesis and production process |
| CN103254115A (en) * | 2013-05-27 | 2013-08-21 | 南通龙翔化工有限公司 | Preparation method of 3-nitro carbazole |
| CN107098848A (en) * | 2017-05-16 | 2017-08-29 | 三峡大学 | A kind of production method of carbazole |
| US10308449B2 (en) | 2016-09-27 | 2019-06-04 | Cargobeamer Ag | Shuttle bar for transport of railcar pallets, freight-handling device, and freight-handling method |
| CN116803498A (en) * | 2023-06-13 | 2023-09-26 | 北京海望氢能科技有限公司 | Dehydrogenation catalyst, preparation method and application thereof in preparation of carbazole through diphenylamine dehydrogenation |
-
2011
- 2011-06-08 CN CN201110151504XA patent/CN102249984A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| E.C.HORNING, ET AL.: "Aromatization Studies.Ⅶ. Alkylcarbazoles", 《J.AM.CHEM.SOC.》 * |
| K.Y.HINDLE ET AL.: "Dramatic liquid-phase dehydrogenation rate enhancements using gas-phase hydrogen acceptors", 《JOURNAL OF CATALYSIS》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103087550A (en) * | 2013-02-05 | 2013-05-08 | 马鞍山金镨新材料科技有限公司 | Permanent violet product synthesis and production process |
| CN103254115A (en) * | 2013-05-27 | 2013-08-21 | 南通龙翔化工有限公司 | Preparation method of 3-nitro carbazole |
| US10308449B2 (en) | 2016-09-27 | 2019-06-04 | Cargobeamer Ag | Shuttle bar for transport of railcar pallets, freight-handling device, and freight-handling method |
| CN107098848A (en) * | 2017-05-16 | 2017-08-29 | 三峡大学 | A kind of production method of carbazole |
| CN107098848B (en) * | 2017-05-16 | 2019-06-11 | 三峡大学 | A kind of production method of carbazole |
| CN116803498A (en) * | 2023-06-13 | 2023-09-26 | 北京海望氢能科技有限公司 | Dehydrogenation catalyst, preparation method and application thereof in preparation of carbazole through diphenylamine dehydrogenation |
| CN116803498B (en) * | 2023-06-13 | 2024-02-13 | 北京海望氢能科技有限公司 | Dehydrogenation catalyst, preparation method and application thereof in preparation of carbazole through diphenylamine dehydrogenation |
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Application publication date: 20111123 |