CN107311932A - A kind of method for catalyzing and synthesizing 1 methylimidazole - Google Patents
A kind of method for catalyzing and synthesizing 1 methylimidazole Download PDFInfo
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- CN107311932A CN107311932A CN201710529293.6A CN201710529293A CN107311932A CN 107311932 A CN107311932 A CN 107311932A CN 201710529293 A CN201710529293 A CN 201710529293A CN 107311932 A CN107311932 A CN 107311932A
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- catalyst
- glyoxal
- ammonia
- methylimidazoles
- paraformaldehyde
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of method for catalyzing and synthesizing 1 methylimidazole.This method is reactant by glyoxal water solution, paraformaldehyde, methylamine water solution and ammonia, it is transition metal oxide carried to synthesize 1 methylimidazole for catalyst, in relatively mild reaction condition and shorter reaction time, 1 methylimidazole is synthesized to higher yields.Meanwhile, catalyst is separated by simply filtering with reaction system, is recycled.
Description
Technical field
The present invention relates to a kind of method for catalyzing and synthesizing 1- methylimidazoles, the present invention provides a kind of supported transition metal oxidation
Thing catalyst, the method for catalyzing and synthesizing 1- methylimidazoles.
Background technology
1- methylimidazoles are also known as N- methylimidazole (English names:1-methylimidazole), its molecular formula is:C4H6N2。
1- methylimidazoles are very important fine chemical material and intermediate, and tool has been widely used, and are widely used in material, doctor
The field such as medicine and agricultural chemicals, such as:As cation parent the ionic liquid that quaterisation synthesizes imidazoles occurs for 1- methylimidazoles;
1- methylimidazoles as medicine intermediate raw material, for preparing Losartan, nitre azoles fragrant ketone and hydrochloric acid naphthalene first imidazoles etc.;In agricultural chemicals
In field, 1- methylimidazoles are widely used in synthesizing fungicide and Plant growth-promoting effect agent.In addition, 1- methylimidazoles also by with
Synthesis and glycolyl catalyst in DNA, curing agent, the adhesive of other resins such as epoxy resin, in cast
Also there is very big application etc. with fiberglass field.Therefore, the synthesis technique of optimization 1- methylimidazoles has fine application value
And Research Significance.
At present, the preparation method research on 1- methylimidazoles focuses primarily upon imidazoles method of substitution and one kettle way, and imidazoles takes
Dai Fawei imidazoles reacts with alkylating reagent, and common alkylating reagent has halide, DMC, methanol etc., but imidazoles method of substitution
Technique is longer, high energy consumption, the use of the higher imidazoles of price is raw material, makes production cost higher, be unfavorable for industrialized production.One pot
Method is predominantly Material synthesis 1- methylimidazoles with glyoxal, formaldehyde, methylamine and ammonia, and patent CN 101633642 describes one kind
The gas and liquid phase method of ammoniacal liquor is replaced with ammonia, the introducing of raw material reclaimed water is reduced, the cost isolated and purified is reduced, but during reaction
Between it is longer（6h）；Patent JP 2013119524 and patent WO 2015015804 disclose it is a kind of using ethylene glycol instead of glyoxal as
Raw material catalyzes and synthesizes 1- methylimidazoles under conditions of catalyst presence, the method use the second two of cheaper green
Alcohol, but the synthetic method yield is relatively low, respectively 12% and 45%；Patent CN 105732508 discloses a kind of vapor phase method catalysis
Prepare 1- methylimidazoles, this method have can continuous operation, the advantages of glyoxal high conversion rate, however, it is necessary to higher temperature
Degree（110-130℃）.Therefore, from industrial practical application and environmental protection theory, it is necessary to develop a class raw material and be easy to get, energy
Low, the environmentally safe synthetic route of consumption, while the separation of catalyst can be facilitated and the reuse of catalyst is realized.
The content of the invention
It is an object of the invention to provide a kind of method for catalyzing and synthesizing 1- methylimidazoles.
The present invention have selected a kind of method that transition metal oxide carried catalysis prepares 1- methylimidazoles, existing to solve
Technology exist the problems such as yield is relatively low and crude product wastewater flow rate is big.
The present invention provides a kind of new synthetic route, is made by glyoxal water solution, paraformaldehyde, methylamine water solution and ammonia
It is transition metal oxide carried to synthesize 1- methylimidazoles for catalyst for reactant, relatively mild reaction condition and compared with
In the short reaction time, 1- methylimidazoles are synthesized to higher yields.Meanwhile, catalyst is by simply filtering and reaction system point
From being recycled.
To solve above-mentioned problem, the technical solution that the present invention is used is as follows：
The reaction equation of the present invention is as follows：
Catalyst represents catalyst in formula
A kind of method for catalyzing and synthesizing 1- methylimidazoles, it is characterised in that use transition metal oxide carried for catalyst, with
Glyoxal water solution, paraformaldehyde, methylamine water solution and ammonia catalyze and synthesize 1- methylimidazoles as reactant；Active constituent
Transition metal oxide be FeOx, CuO or NiO, FeOxMiddle X represents 2 or 3, carrier Al2O3、SiO2Or ZSM-5.
Reaction temperature of the present invention is 25-100 DEG C, and the reaction time is 1~8 h.
Preferable reaction temperature of the present invention is 50-70 DEG C, the h of reaction time 2~6.
The loading of catalyst activity metal oxide of the present invention is 1-20wt.%, is prepared using infusion process.
The consumption of catalyst of the present invention is 1~10 wt.% of glyoxal consumption.
The preferred consumption of catalyst of the present invention is 2~5 wt.% of glyoxal consumption.
Glyoxal of the present invention, paraformaldehyde, the mol ratio of methylamine and ammonia are 1:1-1.5:1-1.5:1-5.
Currently preferred glyoxal, paraformaldehyde, methylamine and ammonia mol ratio are 1:1-1.2:1-1.2:2-4.
Invention using catalysis gas and liquid phase one kettle way, first simultaneously using paraformaldehyde and ammonia replace formalin and
Ammoniacal liquor reduces the introducing of raw material reclaimed water as initiation material, so that purifying cost is reduced, meanwhile, the present invention has target
Products collection efficiency is high, and the reaction time is short, and catalyst cost is low, the advantages of catalyst recyclable recycling, with very strong reality
Application value.
Compared with conventional synthesis 1- methylimidazole routes, the substantive distinguishing features that the present invention has are：
Raw material is easy to get, cheap, and catalyst cost is low；Reaction condition is relatively mild, catalytic activity is high, and product yield is up to
To 90%；Formalin and ammoniacal liquor are replaced using paraformaldehyde and ammonia simultaneously, reduce waste water processing and purifying into
This；Catalyst and reaction system are easy to separation, may be reused, and are easy to amplification and commercial Application.
Embodiment
Embodiment 1：
Weigh 1.99g Ni（NO3）2.6H2O is added in round-bottomed flask, adds 100mL deionized waters, then at ambient temperature
Slow 10g ZSM-5 while stirring（NKF-5-80HW）, continue to stir 12h at ambient temperature after the completion of charging, be put into 80 DEG C
It is dried overnight in baking oven, dries after finishing 500 DEG C of roasting 3h (heating rate of Muffle furnace be 10 DEG C/mins) in Muffle furnace,
Obtain NiO/ZSM-5 catalyst.NiO/Al is made using identical dipping method2O3、CuO/Al2O3、CuO/SiO2、CuO/ZSM-
5 and FeO3/ ZSM-5 catalyst.
Embodiment 2：
It is about that 0.24mol is added in 250mL round-bottomed flasks by 40wt% methylamine water solutions 18g, weighs 7.6g about 0.24mol
Content is more than 95% paraformaldehyde, is slowly added into paraformaldehyde under the water bath condition being sufficiently stirred for water-soluble equipped with methylamine
In the round-bottomed flask of liquid, maintain temperature constant, weigh 40wt.% glyoxal water solutions 29g（0.2mol）It is slowly dropped to
In the round-bottomed flask for adding methylamine water solution and paraformaldehyde, mixed liquor is transferred in 100ml reactors after the completion of charging,
The following border ring of 0.1MPa pressure reacts 4h under the conditions of being passed through ammonia 2h, 65 DEG C of maintenance reaction temperature, and finally obtaining yield is
78%。
Embodiment 3：
Mixed liquor is transferred in 100ml reactors with case study on implementation 2, adds embodiment party by specific charging process after the completion of charging
The NiO/ZSM-5 catalyst 1.2g prepared in case 1, ammonia 2h, maintenance reaction temperature are passed through in the following border ring of 0.1MPa pressure
4h is reacted under the conditions of 65 DEG C of degree, it is 90% to finally obtain yield.
Embodiment 4：
Mixed liquor is transferred in 100ml reactors with case study on implementation 2, adds NiO/ by specific charging process after the completion of charging
Al2O3Catalyst 1.2g, 4h is reacted under the conditions of the following border ring of 0.1MPa pressure is passed through ammonia 2h, 65 DEG C of maintenance reaction temperature,
It is 84% to finally obtain yield.
Embodiment 5：
Mixed liquor is transferred in 100ml reactors, CuO/Al by specific charging process with case study on implementation 2 after the completion of charging2O3
Catalyst 1.2g, reacts 4h, finally under the conditions of the following border ring of 0.1MPa pressure is passed through ammonia 2h, 65 DEG C of maintenance reaction temperature
It is 83% to obtain yield.
Embodiment 6：
Mixed liquor is transferred in 100ml reactors, CuO/SiO by specific charging process with case study on implementation 2 after the completion of charging2Urge
Agent 1.2g, 4h is reacted under the conditions of the following border ring of 0.1MPa pressure is passed through ammonia 2h, 65 DEG C of maintenance reaction temperature, finally
It is 82% to yield.
Embodiment 7：
Mixed liquor is transferred in 100ml reactors with case study on implementation 2, adds CuO/ by specific charging process after the completion of charging
ZSM-5 catalyst 1.2g, react under the conditions of the following border ring of 0.1MPa pressure is passed through ammonia 2h, 65 DEG C of maintenance reaction temperature
4h, it is 85% to finally obtain yield.
Embodiment 8：
Mixed liquor is transferred in 100ml reactors with case study on implementation 2, adds FeO by specific charging process after the completion of chargingx/
ZSM-5 catalyst 1.2g, react under the conditions of the following border ring of 0.1MPa pressure is passed through ammonia 2h, 65 DEG C of maintenance reaction temperature
4h, it is 86% to finally obtain yield.
Claims (8)
1. a kind of method for catalyzing and synthesizing 1- methylimidazoles, it is characterised in that use transition metal oxide carried for catalyst,
Using glyoxal water solution, paraformaldehyde, methylamine water solution and ammonia as reactant, 1- methylimidazoles are catalyzed and synthesized；Activearm
The transition metal oxide of part is FeOx, CuO or NiO, FeOxMiddle X represents 2 or 3, carrier Al2O3、SiO2Or ZSM-5.
2. the method as described in claim 1, it is characterised in that reaction temperature is 25-100 DEG C, the reaction time is 1~8 h.
3. method as claimed in claim 2, it is characterised in that reaction temperature is 50-70 DEG C, the h of reaction time 2~6.
4. the method as described in claim 1, it is characterised in that the loading of catalyst activity metal oxide is 1-20wt.%,
Prepared using infusion process.
5. the method as described in claim 1, it is characterised in that the consumption of catalyst is 1~10 wt.% of glyoxal consumption.
6. method as claimed in claim 5, it is characterised in that catalyst amount is 2~5 wt.% of glyoxal consumption.
7. the method as described in claim 1, it is characterised in that glyoxal, paraformaldehyde, the mol ratio of methylamine and ammonia are 1:
1-1.5:1-1.5:1-5。
8. method as claimed in claim 7, it is characterised in that glyoxal, paraformaldehyde, methylamine and ammonia mol ratio are 1:1-
1.2:1-1.2:2-4。
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002040454A1 (en) * | 1998-06-12 | 2002-05-23 | The Board Of Trustees Of The University Of Alabama | Process for manufacture of imidazoles |
| CN105272918A (en) * | 2015-11-20 | 2016-01-27 | 湘潭大学 | 1-alkyl-3-vinyl-2,4,5-triaryl imidazole halide and preparation method and application |
| CN105732508A (en) * | 2016-03-28 | 2016-07-06 | 南京师范大学 | Continuous preparation method of N-methylimidazole |
-
2017
- 2017-07-01 CN CN201710529293.6A patent/CN107311932A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002040454A1 (en) * | 1998-06-12 | 2002-05-23 | The Board Of Trustees Of The University Of Alabama | Process for manufacture of imidazoles |
| CN105272918A (en) * | 2015-11-20 | 2016-01-27 | 湘潭大学 | 1-alkyl-3-vinyl-2,4,5-triaryl imidazole halide and preparation method and application |
| CN105732508A (en) * | 2016-03-28 | 2016-07-06 | 南京师范大学 | Continuous preparation method of N-methylimidazole |
Non-Patent Citations (6)
| Title |
|---|
| ALI MALEKI ET AL.: "Design, preparation and characterization of urea-functionalized Fe3O4/SiO2 magnetic nanocatalyst and application for the one-pot multicomponent synthesis of substituted imidazole derivatives", 《CATALYSIS COMMUNICATIONS》 * |
| ASHOK V. BORHADE ET AL.: "Synthesis, characterization and catalytic application of silica supported tin oxide nanoparticles for synthesis of 2,4,5-tri and 1,2,4,5-tetrasubstituted imidazoles under solvent-free conditions", 《ARABIAN JOURNAL OF CHEMISTRY》 * |
| KOBRA NIKOOFAR ET AL.: "ZnO nanorods: Efficient and reusable catalysts for the synthesis ofsubstituted imidazoles in water", 《JOURNAL OF TAIBAH UNIVERSITY FOR SCIENCE》 * |
| N. THIMMARAJU ET AL.: "Synthesis of 2,4,5-trisubstituted imidazoles, quinoxalines and 1,5-benzodiazepines over an ecofriendly and highly efficient ZrO2-Al2O3 catalyst", 《RSC ADVANCES》 * |
| 张平 等: "N-甲基咪唑合成工艺研究", 《安徽科技学院学报》 * |
| 朱洪法、朱玉霞主编: "《无机化工产品手册》", 31 December 2008, 金盾出版社 * |
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