CN107935916A - The method that catalytic hydrogenation produces permanent violet intermediate - Google Patents
The method that catalytic hydrogenation produces permanent violet intermediate Download PDFInfo
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- CN107935916A CN107935916A CN201711023893.1A CN201711023893A CN107935916A CN 107935916 A CN107935916 A CN 107935916A CN 201711023893 A CN201711023893 A CN 201711023893A CN 107935916 A CN107935916 A CN 107935916A
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- hydrogen
- nitro
- permanent violet
- carbon catalyst
- platinum carbon
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Indole Compounds (AREA)
Abstract
The invention discloses a kind of method that catalytic hydrogenation produces permanent violet intermediate.The method is by being 1 by mass ratio:The 3 nitro N ethyl carbazoles and o-dichlorohenzene of (1~5), and put into not less than the platinum carbon catalyst of reactant quality 1% in reaction kettle, after being warming up to dissolving, nitrogen displacement, vacuumizes, and is passed through hydrogen, stirring heating, continues logical hydrogen, is reacted at 110~115 DEG C, preserving heat after reaction ends, terminate logical hydrogen, cooling, stand, pressure release, filters platinum carbon catalyst, obtains permanent violet intermediate.The present invention is by under the action of platinum carbon catalyst, the intermediate of permanent violet, energy conservation and environmental protection are prepared using hydrogen and 3 nitro N ethyl carbazoles generation hydrogenation reaction, nitro conversion ratio reaches 99.31%, remain nitro compounds as low as 0.03%, by-products content as low as 0.66%.
Description
Technical field
The invention belongs to organic chemical synthesis field, and in particular to a kind of catalytic hydrogenation produces the side of permanent violet intermediate
Method.
Background technology
Permanent violet RL is the high-grade organic pigment of dioxazine, has prominent tinctorial strength, brightness and excellent resistance to
Hot, resistance to oozing property and good fastness to light, be widely used in coating, plastics, organic glass, rubber, textile printing, solvent inkjet ink,
, also there is application in the fields such as aqueous ink, packages printing in offset printing, gravure, field of flexography.
Traditional produces among permanent violet in body technology, and catalytic hydrogenating reduction reaction is carried out using Raney's nickel as catalyst.
Raney's nickel activity is higher, and it is inflammable to run into air.Directly contact Raney's nickel may result in respiratory inflammation, cause eyes and skin
Irritating infringement, suction can cause the fibrosis of nasal cavity and lung, and intake can then cause to faint from fear and intestines problem, Long Term Contact
It may cause pneumonia and other mark sensitization nickel sample fash, it is all unfriendly to environment and human body.
The content of the invention
It is an object of the invention to provide the high catalytic hydrogenation system of a kind of energy conservation and environmental protection, the reduction of production unit consumption, product quality
The method for taking permanent violet intermediate.
Realize that the technical solution of the object of the invention is as follows：
The method that catalytic hydrogenation produces permanent violet intermediate, using 3- nitro-N- ethyl carbazoles as raw material, is catalyzed using platinum carbon
Agent catalytic hydrogenation produces permanent violet intermediate, and synthetic route is as follows：
Comprise the following steps that：
It is in mass ratio 1 into hydrogenation reaction kettle:(1~5) 3- nitro-N- ethyl carbazoles and o-dichlorohenzene, input are added
Not less than the platinum carbon catalyst of reactant quality 1%, dissolving is warming up to, nitrogen displacement, vacuumizes, and is passed through hydrogen, stirs, and rises
Temperature, continues logical hydrogen, boosts to 0.6MPa, reacted at 110~115 DEG C, and qualified sampling analysis is that reaction terminates, and insulation 1~
2h, terminates logical hydrogen, is cooled to 80~90 DEG C, stands 1~1.5h, pressure release, filters platinum carbon catalyst, obtain among permanent violet
Body.
Preferably, the mass ratio of the 3- nitro-N- ethyl carbazoles and o-dichlorohenzene is 1:2.
Preferably, the platinum content of the platinum carbon catalyst is 1%~3%.
Preferably, the nitrogen displacement number is 3~4 times.
Preferably, the pressure after vacuumizing is 0.06MPa.
Preferably, the reaction time is 15~16h.
Compared with prior art, the present invention is by under the action of platinum carbon catalyst, utilizing hydrogen and 3- nitro-N- ethyls
The intermediate that hydrogenation reaction prepares permanent violet occurs for carbazole.Energy conservation and environmental protection of the present invention, production unit consumption reduce, product quality is high, nitre
Base conversion ratio reaches 99.31%, remains nitro compounds as low as 0.03%, by-products content as low as 0.66%.
Embodiment
With reference to embodiment, the invention will be further described.
Embodiment 1
Nitro compounds (3- nitro-N- ethyl carbazoles) 500g, the o-dichlorohenzene of permanent violet are added into the hydrogenation reaction kettle of 2L
1000g, platinum carbon catalyst 10g (platinum content 1%), are warming up to 60 DEG C of dissolvings.Nitrogen displacement 3 times；Be evacuated to again-
0.06Mpa, closes vacuum, then is passed through hydrogen to 0.1Mpa, opens stirring and hydriding reactor heats up, hydrogen is led into kettle.In pressure
0.6MPa, complete reaction under the conditions of 110 DEG C, when the time about 15 is small；Sampling analysis is qualified, keeps the temperature two hours, terminates logical hydrogen.Will
Hydrogenation kettle is cooled to 80~90 DEG C, when standing 1~1.5 is small；Pressure release emptying simultaneously nitrogen displacement 2 times；Catalyst is filtered out, is obtained forever
Gu purple intermediate.
Embodiment 2
Nitro compounds (3- nitro-N- ethyl carbazoles) 500g, the o-dichlorohenzene of permanent violet are added into the hydrogenation reaction kettle of 2L
500g, platinum carbon catalyst 10g (platinum content 1%), are warming up to 60 DEG C of dissolvings.Nitrogen displacement 3 times；Be evacuated to again-
0.06Mpa, closes vacuum, then is passed through hydrogen to 0.1Mpa, opens stirring and hydriding reactor heats up, hydrogen is led into kettle.In pressure
0.6MPa, complete reaction under the conditions of 110 DEG C, when the time about 15 is small；Sampling analysis is qualified, keeps the temperature two hours, terminates logical hydrogen.Will
Hydrogenation kettle is cooled to 80~90 DEG C, when standing 1~1.5 is small；Pressure release emptying simultaneously nitrogen displacement 2 times；Catalyst is filtered out, is obtained forever
Gu purple intermediate.
Embodiment 3
Nitro compounds (3- nitro-N- ethyl carbazoles) 500g, the o-dichlorohenzene of permanent violet are added into the hydrogenation reaction kettle of 5L
2500g, platinum carbon catalyst 10g (platinum content 3%), are warming up to 60 DEG C of dissolvings.Nitrogen displacement 3 times；Be evacuated to again-
0.06Mpa, closes vacuum, then is passed through hydrogen to 0.1Mpa, opens stirring and hydriding reactor heats up, hydrogen is led into kettle.In pressure
0.6MPa, complete reaction under the conditions of 110 DEG C, when the time about 15 is small；Sampling analysis is qualified, keeps the temperature two hours, terminates logical hydrogen.Will
Hydrogenation kettle is cooled to 80~90 DEG C, when standing 1~1.5 is small；Pressure release emptying simultaneously nitrogen displacement 2 times；Catalyst is filtered out, is obtained forever
Gu purple intermediate.
Comparative example
Nitro compounds (3- nitro-N- ethyl carbazoles) 500g, the o-dichlorohenzene of permanent violet are added into the hydrogenation reaction kettle of 2L
1000g, add Ra-Ni catalyst 20g into hydrogenation kettle, adds ammonium hydroxide 5g, is warming up to 60 DEG C of dissolvings.Nitrogen displacement 3 times；Take out again
Vacuum is to -0.06Mpa, pass vacuum, then is passed through hydrogen to 0.1Mpa, opens stirring and hydriding reactor heats up 75~78 DEG C, lead into kettle
Hydrogen.Reaction is completed under the conditions of 1.0~1.2MPa of pressure, 110~118 DEG C, when the time about 15 is small；Sampling analysis is qualified, protects
Temperature two hours, terminates logical hydrogen.Hydrogenation kettle is cooled to 90 DEG C, when standing 1~1.5 is small；After pressure release emptying and nitrogen displacement 2 times
Emptying, adds the dilution of 500g o-dichlorohenzenes, vacuum filter.Catalyst seal is stand-by, and solution carries out lower step reaction.
The specific experiment data of 1 each embodiment of table and comparative example
Table 1 is each embodiment and the specific experiment data of comparative example.In embodiment 1, nitro compounds and the solvent matter of permanent violet
Amount is than being 1:When 2, nitro conversion ratio is up to 99.31%, and by-products content only has 0.66%, and residual nitro compounds only have 0.03%.It is real
Apply in example 2, nitro compounds and the solvent quality ratio of permanent violet are 1：1, reaction result and 1 indifference of optimal case embodiment, reactant
Concentration increase, reaction speed are accelerated.In embodiment 3, nitro compounds and the solvent quality ratio of permanent violet are 1：5, reaction result and reality
1 indifference of example is applied, reactant concentration reduces, and reaction speed reduces.
In comparative example, catalyst is used as using Raney's nickel.Comparative example and comparative example the result shows that, Raney's nickel is reacting
In effect and carbon load platinum catalyst does not have essential distinction, and total recovery is than using low 1% or so of platinum carbon catalyst.But use
Raney's nickel catalyst, easily forms emulsion layer in process of production, is unfavorable for product separation.In secure context, urged using Raney's nickel
The method of agent, reaction temperature is higher, and reaction pressure is larger, unfavorable to keeping the safety in production, and Raney's nickel belongs to hazardous chemical
It can only be stored in water, water shortage postignition.Raney's nickel is easily attenuated using rear, is easily entrained in material, but activity still exists, and brings into
In later product, easily catch fire, product has security risk when storing.The method adds ammonium hydroxide, and follow-up environmental protection treatment can also be increased
No small pressure.Comparing, the present invention uses platinum carbon catalyst, and safety and environmental protection, production unit consumption is relatively low, and catalyst safety is nontoxic,
Accessible air, facilitates employee to operate, beneficial to large-scale production.
Claims (6)
1. the method that catalytic hydrogenation produces permanent violet intermediate, it is characterised in that comprise the following steps that：
It is in mass ratio 1 into hydrogenation reaction kettle:(1~5) 3- nitro-N- ethyl carbazoles and o-dichlorohenzene are added, input is not small
In the platinum carbon catalyst of reactant quality 1%, dissolving is warming up to, nitrogen displacement, vacuumizes, and is passed through hydrogen, stirs, heating, after
Continuous logical hydrogen, boosts to 0.6MPa, is reacted at 110~115 DEG C, and qualified sampling analysis is that reaction terminates, and keeps the temperature 1~2h, knot
Beam leads to hydrogen, is cooled to 80~90 DEG C, stands 1~1.5h, pressure release, filters platinum carbon catalyst, obtain permanent violet intermediate.
2. according to the method described in claim 1, it is characterized in that, the 3- nitro-N- ethyl carbazoles and o-dichlorohenzene
Mass ratio is 1:2.
3. according to the method described in claim 1, it is characterized in that, the platinum content of the platinum carbon catalyst is 1%~3%.
4. according to the method described in claim 1, it is characterized in that, the nitrogen displacement number is 3~4 times.
5. according to the method described in claim 1, it is characterized in that, the pressure after vacuumizing is 0.06MPa.
6. according to the method described in claim 1, it is characterized in that, the reaction time is 15~16h.
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| CN201711023893.1A CN107935916A (en) | 2017-10-27 | 2017-10-27 | The method that catalytic hydrogenation produces permanent violet intermediate |
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| CN201711023893.1A CN107935916A (en) | 2017-10-27 | 2017-10-27 | The method that catalytic hydrogenation produces permanent violet intermediate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110054582A (en) * | 2019-06-03 | 2019-07-26 | 南通龙翔新材料科技股份有限公司 | A kind of preparation method of 3- amino-N- ethyl carbazole |
| CN112479980A (en) * | 2020-12-14 | 2021-03-12 | 山西紫罗蓝新材料科技有限公司 | Preparation method and application of 3-amino-N-ethyl carbazole |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101544594A (en) * | 2009-05-13 | 2009-09-30 | 南通海迪化工有限公司 | A green catalyzed method for preparing 3-amino-9-ethyl carbazole |
| CN102964278A (en) * | 2012-11-27 | 2013-03-13 | 浙江秦燕化工有限公司 | Method for preparing CLT acid (2-amino-4-methyl-5-chlorobenzene sulfonic acid) by continuous catalytic hydrogenation reduction |
| CN104098474A (en) * | 2014-07-28 | 2014-10-15 | 淮安嘉诚高新化工股份有限公司 | Device and method for producing methyl aniline through performing continuous liquid-phase catalytic hydrogenation reduction on nitrotoluene |
| CN104098477A (en) * | 2014-07-28 | 2014-10-15 | 淮安嘉诚高新化工股份有限公司 | Device and method for production of o-chloroaniline through continuous catalytic hydrogenation reduction of o-nitro chloro benzene |
-
2017
- 2017-10-27 CN CN201711023893.1A patent/CN107935916A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101544594A (en) * | 2009-05-13 | 2009-09-30 | 南通海迪化工有限公司 | A green catalyzed method for preparing 3-amino-9-ethyl carbazole |
| CN102964278A (en) * | 2012-11-27 | 2013-03-13 | 浙江秦燕化工有限公司 | Method for preparing CLT acid (2-amino-4-methyl-5-chlorobenzene sulfonic acid) by continuous catalytic hydrogenation reduction |
| CN104098474A (en) * | 2014-07-28 | 2014-10-15 | 淮安嘉诚高新化工股份有限公司 | Device and method for producing methyl aniline through performing continuous liquid-phase catalytic hydrogenation reduction on nitrotoluene |
| CN104098477A (en) * | 2014-07-28 | 2014-10-15 | 淮安嘉诚高新化工股份有限公司 | Device and method for production of o-chloroaniline through continuous catalytic hydrogenation reduction of o-nitro chloro benzene |
Non-Patent Citations (3)
| Title |
|---|
| 何敬文: "《药物合成》", 30 September 2013, 中国轻工业出版社 * |
| 化学工业部人事教育司等: "《有机化学反应（二）》", 30 June 1997, 化学工业出版社 * |
| 闫江梅等: "Pt/C催化加氢3-氯-4-甲基硝基苯制备3-氯-4-甲基苯胺", 《工业催化》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110054582A (en) * | 2019-06-03 | 2019-07-26 | 南通龙翔新材料科技股份有限公司 | A kind of preparation method of 3- amino-N- ethyl carbazole |
| CN110054582B (en) * | 2019-06-03 | 2022-02-18 | 南通龙翔新材料科技股份有限公司 | Preparation method of 3-amino-N-ethyl carbazole |
| CN112479980A (en) * | 2020-12-14 | 2021-03-12 | 山西紫罗蓝新材料科技有限公司 | Preparation method and application of 3-amino-N-ethyl carbazole |
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