CN103086978B - 1-methylimidazole preparation method - Google Patents
1-methylimidazole preparation method Download PDFInfo
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- CN103086978B CN103086978B CN201310047433.8A CN201310047433A CN103086978B CN 103086978 B CN103086978 B CN 103086978B CN 201310047433 A CN201310047433 A CN 201310047433A CN 103086978 B CN103086978 B CN 103086978B
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- methylimidazole
- fixed bed
- imidazoles
- reaction
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- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 12
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 10
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 10
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 4
- 150000002460 imidazoles Chemical class 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 230000001035 methylating effect Effects 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 abstract description 5
- 238000007069 methylation reaction Methods 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 230000011987 methylation Effects 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000004587 chromatography analysis Methods 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- -1 Glyoxaline compound Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
- 239000002246 antineoplastic agent Substances 0.000 description 1
- 229940041181 antineoplastic drug Drugs 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a 1-methylimidazole preparation method. The method allows 1-methylimidazole to be directly synthesized by adopting a fixed bed continuous flow reaction apparatus and treating ammonium metatungstate exchanged hydrotalcite as a catalyst, imidazole as a raw material and methanol as a methylation reagent, so the method has the advantages of low raw material cost, simple operation, less pollution, high yield and the like, and can easily realize the industrial production.
Description
Technical field
The invention belongs to chemical intermediate synthesis technical field, relate to the preparation method of 1-Methylimidazole.
Background technology
Glyoxaline compound develops the special heterogeneous ring compound of a class formation faster in recent years.Special performance is shown at numerous areas such as high performance composite, biological medicine, dyestuff and anti-corrosion of metal.In traditional medicine industry, imidazoles can as antiviral, anti-tumor drug, can as agricultural bactericide, can as composite material solidification agent, electronics processing and fabricating novel solderability preservative etc.1-Methylimidazole is one of important intermediate of imidazoles, apply very extensive at ionic liquid and epoxy curing agent, its traditional synthetic method has two-step approach and single stage method two kinds of methods to obtain, two-step approach first oxalic dialdehyde is obtained imidazoles with formaldehyde, ammoniacal liquor condensation, 1-Methylimidazole is obtained further again with methyl-sulfate methylation reaction, the method due to methyl-sulfate used be hypertoxic raw material, raw materials cost is also higher; Single stage method be with oxalic dialdehyde, formaldehyde, methylamine, the direct cyclization of ammoniacal liquor and preparing, but the general productivity ratio of method is lower, and by product is many, and separating-purifying is cumbersome.
Summary of the invention
Technical problem to be solved by this invention overcomes the deficiencies in the prior art, provides a kind of method preparing 1-Methylimidazole, the method have pollute little, yield is high, be easy to the feature of suitability for industrialized production.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows:
Prepare a method for 1-Methylimidazole, adopt fixed bed continuous flow reaction unit, with ammonium metawolframate pillared hydrotalcite for catalyzer, being raw material with imidazoles, take methyl alcohol as methylating reagent, directly the obtained 1-Methylimidazole of synthesis.
Wherein, the mol ratio of imidazoles and methyl alcohol is 1:1 ~ 10, and preferred mol ratio is 1:4 ~ 6.
Wherein, reaction conditions is: fixed bed internal pressure 0.1 ~ 1MPa, at 250 ~ 400 DEG C, and reaction solution feedstock quality air speed 0.05 ~ 0.6/h.Preferred reaction conditions is: fixed bed internal pressure 0.4 ~ 0.6MPa, at 320 ~ 350 DEG C, and reaction solution feedstock quality air speed 0.3 ~ 0.4/h.
The concrete reaction equation of the inventive method is as follows:
After above-mentioned building-up reactions terminates, use water distilling apparatus, be collected in the fraction of 100-110 DEG C (4.0kPa), until cut temperature reaches 110 DEG C, no longer include cut and reserve, stop distillation, highly purified 1-Methylimidazole can be obtained.
Ammonium metawolframate pillared hydrotalcite catalyzer of the present invention has special laminate structure, has good catalytic activity, specifically synthesizes see document [Zhu little Mei, Zou Xiujing, Wang Zhen trip, etc. Dalian Maritime University's journal, 2008,34 (1), 107-111], specific as follows:
In there-necked flask, first add a certain amount of water, be warming up to 75 DEG C, more slowly drip two parts of solution simultaneously, portion is the mixing solutions of magnesium nitrate and aluminum nitrate, portion is sodium hydroxide solution, controls rate of addition, and insulated and stirred 12 hours again after dripping off, is then chilled to room temperature, filter, washing, obtains solid.The solid water dissolution of above-mentioned preparation disperseed, stirring at room temperature 10 hours, then to add dust technology regulator solution pH be 6, be warming up to 75 DEG C, under agitation add ammonium metatungstate solution, insulation reaction 2 hours, filter, washing, obtains ammonium metawolframate pillared hydrotalcite.
Beneficial effect: the present invention has following obvious advantage:
1, synthetic method of the present invention adopts fixed bed continuous processing, easy and simple to handle, pollute less, yield advantages of higher, be easy to suitability for industrialized production.
2, the present invention adopts methyl alcohol to be methylating reagent, and raw materials cost is low, and toxicity is little.
3, the present invention adopts ammonium metawolframate pillared hydrotalcite to be catalyzer, and catalytic activity is high, and environmental pollution is little, long service life.
Embodiment
According to following embodiment, the present invention may be better understood.But those skilled in the art will readily understand, concrete material proportion, processing condition and result thereof described by embodiment only for illustration of the present invention, and should can not limit the present invention described in detail in claims yet.
Embodiment 1:
100ml water is first added in there-necked flask, be warming up to 75 DEG C, more slowly drip two parts of solution simultaneously, portion is the mixing solutions of 217g17.9% magnesium nitrate (0.15mol) and 13.1% aluminum nitrate (0.15mol), portion is 175g14.3% sodium hydroxide (0.6mol) solution, control rate of addition, maintenance pH value of solution is 8-10, insulated and stirred 12 hours again after dripping off, then room temperature is chilled to, filter, washing, obtains solid 25.6g.
The 10.0g 100ml water dissolution of above-mentioned preparation is disperseed, stirring at room temperature 10 hours, adding 0.2mol/L dust technology regulator solution pH is again 6, be warming up to 75 DEG C, under agitation add 100ml0.08mol/L ammonium metatungstate solution, insulation reaction 2 hours, filter, washing, obtains solid ammonium metawolframate pillared hydrotalcite 18.7g.
Embodiment 2:
Reaction is carried out on fixed bed continuous flow reaction unit, fixed bed internal pressure 0.5MPa, catalyzer ammonium metawolframate pillared hydrotalcite consumption 1.4g, temperature of reaction 330 DEG C, reaction solution imidazoles and methanol molar ratio 1:5, reaction solution feedstock quality air speed 0.34/h, outlets products is after collecting, use water distilling apparatus, be collected in the fraction of 100-110 DEG C (4.0kPa), until cut temperature reaches 110 DEG C, no longer include cut to reserve, stop distillation, product yield 92%, content is through gas chromatographic analysis 99%.
Embodiment 3:
Reaction is carried out on fixed bed continuous flow reaction unit, fixed bed internal pressure 0.1MPa, catalyzer ammonium metawolframate pillared hydrotalcite consumption 1.4g, temperature of reaction 250 DEG C, reaction solution imidazoles and methanol molar ratio 1:1, reaction solution feedstock quality air speed 0.4/h, outlets products is after collecting, use water distilling apparatus, be collected in the fraction of 100-110 DEG C (4.0kPa), until cut temperature reaches 110 DEG C, no longer include cut to reserve, stop distillation, product yield 83%, content is through gas chromatographic analysis 99%.
Embodiment 4:
Reaction is carried out on fixed bed continuous flow reaction unit, fixed bed internal pressure 1MPa, catalyzer ammonium metawolframate pillared hydrotalcite consumption 1.4g, temperature of reaction 400 DEG C, reaction solution imidazoles and methanol molar ratio 1:10, reaction solution feedstock quality air speed 0.6/h, outlets products is after collecting, use water distilling apparatus, be collected in the fraction of 100-110 DEG C (4.0kPa), until cut temperature reaches 110 DEG C, no longer include cut to reserve, stop distillation, product yield 91%, content is through gas chromatographic analysis 99%.
Claims (1)
1. prepare a method for 1-Methylimidazole, it is characterized in that, adopt fixed bed continuous flow reaction unit, with ammonium metawolframate pillared hydrotalcite for catalyzer, being raw material with imidazoles, take methyl alcohol as methylating reagent, directly the obtained 1-Methylimidazole of synthesis;
Wherein, the mol ratio of imidazoles and methyl alcohol is 1:1 ~ 10;
Wherein, fixed bed internal pressure 0.1 ~ 1MPa, at 250 ~ 400 DEG C, reaction solution feedstock quality air speed 0.05 ~ 0.6/h;
Wherein, after building-up reactions terminates, use water distilling apparatus, be collected in 4.0kPa, the fraction of 100 ~ 110 DEG C, until cut temperature reaches 110 DEG C, no longer include cut and flow out, stop distillation, 1-Methylimidazole can be obtained.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310047433.8A CN103086978B (en) | 2013-02-06 | 2013-02-06 | 1-methylimidazole preparation method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310047433.8A CN103086978B (en) | 2013-02-06 | 2013-02-06 | 1-methylimidazole preparation method |
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| Publication Number | Publication Date |
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| CN103086978A CN103086978A (en) | 2013-05-08 |
| CN103086978B true CN103086978B (en) | 2015-03-04 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110343071A (en) * | 2019-08-05 | 2019-10-18 | 宁夏倬昱新材料科技有限公司 | A kind of purifying process of 1- methylimidazole |
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Address after: 224000 Zhongshan Third Road, Binhai Chemical Park, Yancheng City, Jiangsu Province Patentee after: JIANGSU CALE NEW MATERIAL CO.,LTD. Address before: 224000 Zhongshan Third Road, Binhai Chemical Park, Yancheng City, Jiangsu Province Patentee before: JIANGSU CALE NEW MATERIALS Co.,Ltd. |
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Effective date of registration: 20191227 Address after: Room 1508, enterprise headquarters, Ningdong Town, Lingwu City, Yinchuan City, Ningxia Hui Autonomous Region Patentee after: NINGXIA ZHUOYU NEW MATERIAL TECHNOLOGY Co.,Ltd. Address before: 224000 Binhai chemical industry zone, Binhai County, Jiangsu, Zhongshan three, Yancheng City Patentee before: JIANGSU CALE NEW MATERIAL CO.,LTD. |
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Denomination of invention: A method for preparing 1-Methylimidazole Effective date of registration: 20210927 Granted publication date: 20150304 Pledgee: Ningxia East Guarantee Co.,Ltd. Pledgor: NINGXIA ZHUOYU NEW MATERIAL TECHNOLOGY Co.,Ltd. Registration number: Y2021640000005 |
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Date of cancellation: 20221108 Granted publication date: 20150304 Pledgee: Ningxia East Guarantee Co.,Ltd. Pledgor: NINGXIA ZHUOYU NEW MATERIAL TECHNOLOGY Co.,Ltd. Registration number: Y2021640000005 |
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Denomination of invention: A method for preparing 1-methylimidazole Effective date of registration: 20230109 Granted publication date: 20150304 Pledgee: Ningxia East Guarantee Co.,Ltd. Pledgor: NINGXIA ZHUOYU NEW MATERIAL TECHNOLOGY Co.,Ltd. Registration number: Y2023640000004 |