CN103254115A - Preparation method of 3-nitro carbazole - Google Patents
Preparation method of 3-nitro carbazole Download PDFInfo
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- CN103254115A CN103254115A CN2013101995900A CN201310199590A CN103254115A CN 103254115 A CN103254115 A CN 103254115A CN 2013101995900 A CN2013101995900 A CN 2013101995900A CN 201310199590 A CN201310199590 A CN 201310199590A CN 103254115 A CN103254115 A CN 103254115A
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Abstract
The invention relates to a preparation method of 3-nitro carbazole, which comprises the following steps: adding an organic solvent, 3-nitro tetrahydrocarbazole and a catalyst into a reactor with a stirring and reflux condenser, and heating the obtained mixture so as to remove low-boiling-point substances; continuing to heat the obtained object to 140-350 DEG C to carry out a reaction, and after the 3-nitro tetrahydrocarbazole conversion rate is more than 99%, obtaining reaction liquid; filtrating the reaction liquid, and recovering the catalyst; carrying out distillation on filter liquor so as to recover the organic solvent; and carrying out cooling crystallization, filter washing and drying on the obtained product so as to obtain 3-nitro carbazole. The method disclosed by the invention has the advantages of simple process, relatively mild conditions, high conversion rate, and easiness for product separation and purification.
Description
Technical field
The present invention relates to a kind of preparation method of 3-nitro carbazole, belong to chemical field.
Background technology
3-nitro-N-ethyl carbazole is the important intermediate of synthetic high-grade pigment dyestuff permanent violet RL, under the effect of phase-transfer catalyst, generate N-ethyl carbazole with the monobromethane reaction by carbazole, make through rare nitric acid nitrating again, two step total recoverys are no more than 75%, and this method is subjected to carbazole source and the dual restriction of synthesis yield.If can be by chemical method with the synthetic 3-nitro carbazole of non-carbazoles raw material, the preparation 3-nitro-N-ethyl carbazole that ethylizes have again not only been broken away from former technology to the dependence of raw material carbazole, and can be by the optimization and improvement reaction yield.Chinese patent CN102249984 provides a kind of tetrahydro carbazole catalytic dehydrogenation to prepare the method for carbazole, but the synthetic method of 3-nitro carbazole is not appeared in the newspapers as yet.
Summary of the invention
The preparation method who the purpose of this invention is to provide the 3-nitro carbazole that a kind of technology is simple, 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 3-nitro carbazole, may further comprise the steps: in the reactor of band stirring and reflux exchanger, add organic solvent, 3-nitro tetrahydro carbazole and catalyzer, heating up earlier removes low-boiling-point substance, continues to be warming up to 140-250 ℃ and reacts, until 3-nitro tetrahydro carbazole transformation efficiency more than 99%, get reaction solution, with reacting liquid filtering, reclaim catalyzer, organic solvent is reclaimed in the filtrate distillation, again through crystallisation by cooling, diafiltration, the dry 3-nitro carbazole that gets.
A kind of preparation method of 3-nitro carbazole, may further comprise the steps: in the reactor of band stirring and reflux exchanger, add 3-nitro tetrahydro carbazole, after the intensification fusing, add catalyzer, heat up then and remove low-boiling-point substance, continue to be warming up to 200-350 ℃ and react, until 3-nitro tetrahydro carbazole transformation efficiency more than 99%, be cooled in 250 ℃, add organic solvent, after the heating for dissolving, get reaction solution, with reacting liquid filtering, reclaim catalyzer, organic solvent is reclaimed in the filtrate distillation, again through crystallisation by cooling, diafiltration, the dry 3-nitro 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 3-nitro tetrahydro carbazole and organic solvent is 1:2-20.
Described catalyzer is a kind of in load platinum, supported palladium, the Lei Shi nickel, 3-nitro tetrahydro carbazole and give money as a gift after catalyst quality than being 10-1000:1, preferred 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%, preferred 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 restriction of we.
Embodiment 1
In the flask of band stirring and reflux exchanger, adding 200g dimethylbenzene, 20g 3-nitro tetrahydro carbazole, 0.2g charge capacity are platinum/activated carbon catalyst (moisture 50%) of 10%, dehydration heats up earlier, continuing to be warming up to 140 ℃ reacts, until 3-nitro 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 18.8g 3-nitro carbazole, the content 99.3% of getting.
Embodiment 2
In the flask of band stirring and reflux exchanger, add 40g N, dinethylformamide, 20g 3-nitro tetrahydro carbazole, 0. 04g charge capacity are platinum/gold/mesoporous carbon catalyst (moisture 50%) of 20%, and the dehydration that heats up earlier continues to be warming up to 150 ℃ and reacts, until 3-nitro 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 18.5g 3-nitro carbazole, the content 99.8% of getting.
Embodiment 3
In the flask of band stirring and reflux exchanger, adding 100g N-Methyl pyrrolidone, 20g 3-nitro tetrahydro carbazole, 4g charge capacity are palladium/activated carbon catalyst (moisture 50%) of 0.5%, dehydration heats up earlier, continuing to be warming up to 200 ℃ reacts, until 3-nitro 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 18.5g 3-nitro carbazole, the content 98.7% of getting.
Embodiment 4
In the flask of band stirring and reflux exchanger, add 400g orthodichlorobenzene, 20g 3-nitro tetrahydro carbazole, 2g Lei Shi nickel (containing ethanol 50%), heat up earlier and take off ethanol, continuing to be warming up to 180 ℃ reacts, until 3-nitro 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 17.2g 3-nitro carbazole, the content 98.8% of getting.
Embodiment 5
In the flask of band stirring and reflux exchanger, adding 300g trichlorobenzene, 20g 3-nitro tetrahydro carbazole, 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 3-nitro 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 18.7g 3-nitro carbazole, the content 99.1% of getting.
Embodiment 6
In the flask of band stirring and reflux exchanger, adding 300g trichlorobenzene, 20g 3-nitro tetrahydro carbazole, 0.5g charge capacity are palladium/gold/mesoporous carbon catalyst (moisture 50%) of 15%, dehydration heats up earlier, continuing to be warming up to 220 ℃ reacts, until 3-nitro 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 19.2g 3-nitro carbazole, the content 99.7% of getting.
Embodiment 7
In the flask of band stirring and reflux exchanger, add 200g 3-nitro tetrahydro carbazole, the fusing back adding 5g 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 3-nitro 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 186.1g 3-nitro carbazole, the content 99.3% of getting.
Embodiment 8
In the flask of band stirring and reflux exchanger, add 200g 3-nitro tetrahydro carbazole, the fusing back adding 0.4g charge capacity that heats up is palladium/gold/mesoporous carbon catalyst (moisture 50%) of 20%, dehydration heats up earlier, continuing to be warming up to 250 ℃ gradually reacts, until 3-nitro tetrahydro carbazole transformation efficiency more than 99%, be cooled to 140 ℃, add the 800g orthodichlorobenzene, after the heating for dissolving, the reacting liquor while hot filtering recovering catalyst, orthodichlorobenzene is reclaimed in the filtrate distillation, again through crystallisation by cooling, diafiltration, dry 185.5g 3-nitro carbazole, the content 99.1% of getting.
Embodiment 9
In the flask of band stirring and reflux exchanger, add 200g 3-nitro tetrahydro carbazole, the fusing back adding 10g charge capacity that heats up is platinum/aluminium oxide catalyst (moisture 50%) of 1%, dehydration heats up earlier, continuing to be warming up to 300 ℃ gradually reacts, until 3-nitro tetrahydro carbazole transformation efficiency more than 99%, be cooled to 200 ℃, add the 500g N-Methyl pyrrolidone, after the heating for dissolving, the reacting liquor while hot filtering recovering catalyst, N-Methyl pyrrolidone is reclaimed in the filtrate distillation, again through crystallisation by cooling, diafiltration, dry 190.0g 3-nitro carbazole, the content 99.2% of getting.
Embodiment 10
In the flask of band stirring and reflux exchanger, add 200g 3-nitro tetrahydro carbazole, fusing back adding 20g 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 3-nitro tetrahydro carbazole transformation efficiency more than 99%, be cooled to 220 ℃, add the 800g trichlorobenzene, after the heating for dissolving, the reacting liquor while hot filtering recovering catalyst, trichlorobenzene is reclaimed in the filtrate distillation, again through crystallisation by cooling, diafiltration, dry 186.8g 3-nitro carbazole, the content 99.0% 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 3-nitro carbazole, it is characterized in that, may further comprise the steps: in the reactor of band stirring and reflux exchanger, add organic solvent, 3-nitro tetrahydro carbazole and catalyzer, heat up earlier and remove low-boiling-point substance, continue to be warming up to 140-250 ℃ and react, more than 99%, get reaction solution until 3-nitro 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 3-nitro carbazole that gets.
2. the preparation method of a 3-nitro carbazole, it is characterized in that, may further comprise the steps: in the reactor of band stirring and reflux exchanger, add 3-nitro 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,, be cooled in 250 ℃ more than 99% until 3-nitro tetrahydro carbazole transformation efficiency, add organic solvent, after the dissolving, get reaction solution, with reacting liquid filtering, reclaim catalyzer, organic solvent is reclaimed in the filtrate distillation, again through crystallisation by cooling, diafiltration, the dry 3-nitro carbazole that gets.
3. the preparation method of a kind of 3-nitro 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 3-nitro tetrahydro carbazole and solvent is 1:2-20.
4. the preparation method of a kind of 3-nitro 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, 3-nitro tetrahydro carbazole and give money as a gift after catalyst quality than being 10-1000:1.
5. the preparation method of a kind of 3-nitro carbazole according to claim 4 is characterized in that: described 3-nitro tetrahydro carbazole and give money as a gift after catalyst quality than being 50-200:1.
6. the preparation method of a kind of 3-nitro 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 3-nitro carbazole according to claim 6, it is characterized in that: charge capacity is 3%-10%.
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| CN2013101995900A CN103254115A (en) | 2013-05-27 | 2013-05-27 | Preparation method of 3-nitro carbazole |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102249984A (en) * | 2011-06-08 | 2011-11-23 | 南通龙翔化工有限公司 | Preparation method of carbazole |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102249984A (en) * | 2011-06-08 | 2011-11-23 | 南通龙翔化工有限公司 | Preparation method of carbazole |
Non-Patent Citations (2)
| Title |
|---|
| CORNELIU .MINCA等: ""Dyes Derived from Carbazole"", 《REV.CHIM.(BUCURESTI)》 * |
| E.C.HORNING等: ""Aromatization Studies.Ⅶ. Alkylcarbazoles"", 《J.AM.CHEM.SOC.》 * |
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Application publication date: 20130821 |