CN1199935C - Production process of catalytically hydrogenating nitrobenzene halide to synthesize haloarylamine - Google Patents
Production process of catalytically hydrogenating nitrobenzene halide to synthesize haloarylamine Download PDFInfo
- Publication number
- CN1199935C CN1199935C CN 02148509 CN02148509A CN1199935C CN 1199935 C CN1199935 C CN 1199935C CN 02148509 CN02148509 CN 02148509 CN 02148509 A CN02148509 A CN 02148509A CN 1199935 C CN1199935 C CN 1199935C
- Authority
- CN
- China
- Prior art keywords
- hydrogenation
- halogenated
- chloronitrobenzene
- nitrobenzene
- shortening
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000004519 manufacturing process Methods 0.000 title claims description 13
- -1 nitrobenzene halide Chemical class 0.000 title description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Substances [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 title 1
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 150000005181 nitrobenzenes Chemical class 0.000 claims abstract description 13
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 9
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 claims abstract description 8
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 claims abstract description 6
- DPHCXXYPSYMICK-UHFFFAOYSA-N 2-chloro-1-fluoro-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(F)C(Cl)=C1 DPHCXXYPSYMICK-UHFFFAOYSA-N 0.000 claims abstract description 5
- NTBYINQTYWZXLH-UHFFFAOYSA-N 1,2-dichloro-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C(Cl)=C1 NTBYINQTYWZXLH-UHFFFAOYSA-N 0.000 claims abstract description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 20
- 238000004904 shortening Methods 0.000 claims description 15
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 8
- 229910021392 nanocarbon Inorganic materials 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 abstract description 11
- 238000005695 dehalogenation reaction Methods 0.000 abstract description 10
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 6
- 239000007791 liquid phase Substances 0.000 abstract description 2
- 229910052763 palladium Inorganic materials 0.000 abstract description 2
- 229910052697 platinum Inorganic materials 0.000 abstract description 2
- 150000004982 aromatic amines Chemical class 0.000 abstract 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000006298 dechlorination reaction Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000003814 drug Substances 0.000 description 3
- 125000001475 halogen functional group Chemical group 0.000 description 3
- 239000003905 agrochemical Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YSEMCVGMNUUNRK-UHFFFAOYSA-N 3-chloro-4-fluoroaniline Chemical compound NC1=CC=C(F)C(Cl)=C1 YSEMCVGMNUUNRK-UHFFFAOYSA-N 0.000 description 1
- BLNVISNJTIRAHF-UHFFFAOYSA-N 4-chlorobenzamide Chemical compound NC(=O)C1=CC=C(Cl)C=C1 BLNVISNJTIRAHF-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 229960005081 diclofenamide Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a producing method for synthesizing halogenated arylamine from halogenated nitrobenzene through catalytic hydrogenation, which comprises: nanometer carbon tubes are used for carrying Pd, Pt is used as a hydrogenation catalyst, and corresponding halogenated arylamine is synthesized through the liquid phase catalytic hydrogenation of halogenated nitrobenzene, comprising o-chloronitrobenzene, p-chloronitrobenzene, 3, 4-dichloronitrobenzene, 3-chloro-4-fluoronitrobenzene, etc. The producing method can effectively inhibit hydrogenation dehalogenation and has the advantages of favorable selectivity, high yield, high catalyst stability, etc. The producing method has great implementation value and social and economic benefits.
Description
Technical field
The present invention relates to the production method of halogenated nitrobenzene shortening synthesizing halogen aniline, be characterized in adopting nano-carbon tube load Pd, Pt is a hydrogenation catalyst, halogenated nitrobenzene is carried out liquid phase catalytic hydrogenation reaction synthesizing halogen aniline, adopt this production method can effectively suppress hydrodehalogenation, and advantage such as the selectivity of this production method is good, yield is high and catalyst stability is good.Halo aniline is the intermediate of important medicine, agricultural chemicals, dyestuff and daily-use chemical industry, and shortening synthesizing halogen aniline has important economic results in society.
Technical background
Halo aniline is the important chemical intermediate of medicine, agricultural chemicals, dyestuff, spices etc., and purposes is very extensive.The synthetic method of halo aniline has iron powder reducing method, sodium sulfide reducing method and shortening method usually, the first two kind method meeting serious environment pollution, and the shortening method is environmentally friendly relatively, is present method in common.But the shortening method has been run into serious dehalogenation problem.Address this problem two approach are arranged usually: (1) adds the dehalogenation inhibitor in the shortening system; (2) improve the performance of catalyzer, reach the purpose that suppresses dehalogenation.For example U.S. Pat 4070401 discloses the halogenated nitrobenzene catalytic hydrogenation process, in reaction system, added polyamine, it at 100 ℃, hydrogen pressure reaction 150 minutes under the condition of 5.0MPa, the dehalogenation rate is 0.4%, owing in reaction system, introduced the dehalogenation inhibitor, increase production cost, and reduced the quality of product.US5554573 is with improved Renay-Ni hydrogenation catalyst, in the alloy of Ni/Al=1, add Mo, preparation and obtain the Renay-Ni/Mo hydrogenation catalyst, remaining Al has bigger influence to catalytic activity and selectivity, this patent is the hydrogenation object with 3-chloro-4-fluoronitrobenzene, be to react under the condition of 1.8Mpa at 60 ℃, hydrogen pressure, the dehalogenation rate is between 0.4-3.5%.This hydrogenation catalyst is subjected to the influence of Al, and catalytic activity is littler than Renay-Ni, and high active of hydrogenation catalysis descends very fast in reaction process, therefore the catalyzer usage quantity of unit product is higher, increase production cost, and dehalogenation is also comparatively serious, reduces quality product.The applicant discloses Pd-Fe-Ce ternary hydrogenation catalyst in the tenth phase of " Chinese Journal of Pharmaceuticals " calendar year 2001, is used for the o-chloronitrobenzene hydrogenation reaction, and hydrogenation temperature is 80 ℃, and hydrogen pressure is 1.0Mpa, and glue halogen rate is 1.5%.
Summary of the invention
Be easy to generate the shortcoming of hydrodehalogenation and improve halogenated nitrobenzene catalytic hydrogenation reaction yield in order to overcome the halogenated nitrobenzene shortening, the invention provides and a kind ofly can suppress hydrodehalogenation, and can obtain the production method of the halogenated nitrobenzene shortening synthesizing halogen aniline of high yield.
This production method is to be raw material with the halogenated nitrobenzene, and nano-carbon tube load Pd or nano-carbon tube load Pt are hydrogenation catalyst, shortening synthesizing halogen aniline.Halogenated nitrobenzene is o-chloronitrobenzene or parachloronitrobenzene or 3,4-dichloronitrobenzene or 3-chloro-4-fluoronitrobenzene.
Adopt this production method can effectively suppress hydrodehalogenation, and have catalyst activity height, advantage that selectivity is good.Adopt this production method can make the hydrodehalogenation rate less than 0.1%, yield reaches more than 99%.Compared with prior art, the dehalogenation rate can drop to below 0.1% from 10%, and yield can be brought up to more than 99% from about 90%.
Embodiment
Embodiment 1
The catalytic hydrogenation reaction of o-chloronitrobenzene.In 500ml stainless steel high-pressure reactor, add 56g o-chloronitrobenzene, 0.45g nano-carbon tube load Pd catalyzer, dehydrated alcohol 150ml, the off-response device is used nitrogen replacement air 3 times, and each 0.2Mpa uses hydrogen exchange nitrogen three times again, each 0.2Mpa.Add hydrogen to 1.0Mpa, be warming up to 80 ℃ again, start stirring, hydrogen in the reactor is reduced to 0.5Mpa, adds hydrogen again to 1.0Mpa, reaction 90min, and not inhale hydrogen in 15min subsequently be stopped reaction, open reactor, take out reaction solution, filter out catalyzer, filtrate is with each components contents of gas chromatographic analysis, the result shows that the yield of Ortho-Chloro aniline is 99.2%, and dechlorination rate is 0.02%.
Embodiment 2
The raw material of shortening is a parachloronitrobenzene, and hydrogenation catalyst and hydrogenation conditions are with embodiment 1, and the yield of p-Chlorobenzoic acid amide is 99.0%, and dechlorination rate is 0.10%.
Embodiment 3
The raw material of shortening is 3, the 4-dichloronitrobenzene, and hydrogenation catalyst and hydrogenation conditions are with embodiment 1,3, and 4-dichlorphenamide bulk powder yield is 99.2%, and dechlorination rate is 0.1%.
Embodiment 4
The raw material of shortening is a 3-chloro-4-fluoronitrobenzene, and hydrogenation catalyst and hydrogenation conditions are with embodiment 1, and the yield of 3-chloro-4-fluoroaniline is 99.2%, and defluorinate is 0.03%, and dechlorination is 0.06%.
Embodiment 5
Adopt nano-carbon tube load Pt catalyzer, to o-chloronitrobenzene or parachloronitrobenzene or 3, the hydrogenation conditions of 4-dichloronitrobenzene or 3-chloro-4-fluoro-oil of mirbane is with embodiment 1.Reaction result is listed in table.
| Hydrogenating materials | Product yield % | Dehalogenation rate % | |
| O-chloronitrobenzene | 99.1 | 0.01 | |
| Parachloronitrobenzene | 99.3 | 0.06 | |
| 3, the 4-dichloronitrobenzene | 99.0 | 0.05 | |
| 3-chloro-4-fluoro-oil of mirbane | 99.2 | 0.08 |
Claims (2)
1, the production method of halogenated nitrobenzene shortening synthesizing halogen aniline is characterized in that with the halogenated nitrobenzene being raw material, and nano-carbon tube load Pd or nano-carbon tube load Pt are hydrogenation catalyst, shortening synthesizing halogen aniline.
2, production method as claimed in claim 1 is characterized in that halogenated nitrobenzene is o-chloronitrobenzene or parachloronitrobenzene or 3,4-dichloronitrobenzene or 3-chloro-4-fluoronitrobenzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02148509 CN1199935C (en) | 2002-12-09 | 2002-12-09 | Production process of catalytically hydrogenating nitrobenzene halide to synthesize haloarylamine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02148509 CN1199935C (en) | 2002-12-09 | 2002-12-09 | Production process of catalytically hydrogenating nitrobenzene halide to synthesize haloarylamine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1506348A CN1506348A (en) | 2004-06-23 |
| CN1199935C true CN1199935C (en) | 2005-05-04 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02148509 Expired - Fee Related CN1199935C (en) | 2002-12-09 | 2002-12-09 | Production process of catalytically hydrogenating nitrobenzene halide to synthesize haloarylamine |
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| Country | Link |
|---|---|
| CN (1) | CN1199935C (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100369673C (en) * | 2006-03-21 | 2008-02-20 | 浙江工业大学 | Production of 3,4-dichloroaniline catalyst with 3,4-mirbane oil dichloride hydrogenation |
| CN102786424B (en) * | 2012-08-22 | 2014-09-03 | 中国中化股份有限公司 | Method for preparing 3-chloro-4-methylaniline through catalytic hydrogenation |
| CN103113233A (en) * | 2013-01-11 | 2013-05-22 | 山东富原化工有限公司 | Production method for preparing chlorinated aniline via chlorination of nitrobenzene hydrogenation by utilizing solvent-free process |
| CN103467308B (en) * | 2013-09-18 | 2015-08-12 | 葫芦岛天启晟业化工有限公司 | Anti-dechlorinating agent is not used to produce the method for 2,5-dichlorphenamide bulk powder |
| CN103497112B (en) * | 2013-09-18 | 2015-07-22 | 葫芦岛天启晟业化工有限公司 | Method for preparing p-chloroaniline without adding organic solvent |
| CN103524357B (en) * | 2013-09-18 | 2015-11-25 | 葫芦岛天启晟业化工有限公司 | Anti-dechlorinating agent is not used to produce p-Chlorobenzoic acid amide method |
| CN109305922B (en) * | 2017-07-28 | 2021-11-12 | 中国石油化工股份有限公司 | Synthesis method of aminophenol compound |
| CN108821981A (en) * | 2018-05-03 | 2018-11-16 | 浙江解氏新材料股份有限公司 | A kind of catalytic hydrogenation process of the nitroaromatic containing chlorine |
| CN110116018B (en) * | 2019-04-15 | 2020-06-12 | 中国科学院化学研究所 | Noble metal-coated silicon molecular sieve catalytic material and preparation method thereof |
| CN110627652A (en) * | 2019-08-27 | 2019-12-31 | 浙江工业大学 | Application of carbon nano tube embedded metal particle catalyst in reaction of synthesizing halogenated aniline by selective catalytic hydrogenation of halogenated nitrobenzene |
| CN112547124B (en) * | 2019-10-28 | 2022-03-01 | 中国科学技术大学 | Selective hydrogenation catalyst for halogenated nitrobenzene, preparation method thereof and method for catalyzing selective hydrogenation of halogenated nitrobenzene |
-
2002
- 2002-12-09 CN CN 02148509 patent/CN1199935C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN1506348A (en) | 2004-06-23 |
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