CN105367499A - Preparation method of 2-ethyl-4-methylimidazole - Google Patents
Preparation method of 2-ethyl-4-methylimidazole Download PDFInfo
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- CN105367499A CN105367499A CN201510982506.1A CN201510982506A CN105367499A CN 105367499 A CN105367499 A CN 105367499A CN 201510982506 A CN201510982506 A CN 201510982506A CN 105367499 A CN105367499 A CN 105367499A
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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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Abstract
The invention discloses a preparation method of 2-ethyl-4-methylimidazole. The preparation method comprises steps as follows: diamine and propionitrile have a cyclization reaction sequentially at the temperature of 80-110 DEG C and 120-140 DEG C under the catalysis of a catalyst; a product after the cyclization reaction has a dehydrogenation reaction through raney nickel at the temperature of 170-200 DEG C, and 2-ethyl-4-methylimidazole is obtained. The preparation method has the advantages that 2-ethyl-4-methylimidazole is prepared with a substep method, the process cost is reduced, the reaction process is optimized, the operation is simple and convenient, the pollution is reduced, and the reaction yield is high.
Description
Technical field
The invention belongs to a kind of chemical intermediate synthesis technical field of imidazoles product, be specifically related to a kind of preparation method of 2-ethyl-4-methylimidazole.
Background technology
Imidazole and its derivants is a very important based epoxy resin curing agent, and purposes is wide, and usage quantity is large, has good solidification and short curing characteristic, significantly can reduce the temperature of curing reaction, have consumption few, the features such as middle temperature is curable, and the room temperature usage period is longer.2-ethyl-4-methylimidazole is as one of important intermediate of imidazoles, it has outside the advantage of general imidazole curing agent, can also occur with the state of supercooled liquid at normal temperatures, the compatibility of it and epoxy resin and acid anhydride type curing agent is good, technological operation is convenient, and this product receives good evaluation as epoxy curing agent or promotor.
At present, in conjunction with the synthesis mechanism of imidazolium compounds that C-alkyl replaces, what the synthetic route of external 2-ethyl-4-methylimidazole adopted mainly contains two, and namely under pt-Al2O3 exists, carry out cyclisation with diamine and acylating agent, dehydrogenation reaction is obtained; Under sulphur exists, carry out ring-closure reaction with diamine and nitrile, after adding zinc powder sulphur removal, distill to obtain tetrahydroglyoxaline, then dehydrogenation under nickel catalyzator.Organic chemistry magazine J.org.chem., 12 (1947), JACS J.Am.Chem.Soc., 68 (1946) synthetic methods also disclosing this product, there is the shortcomings such as yield is low, by product is many, purification difficult in above preparation method mostly.
Summary of the invention
Technical problem to be solved by this invention overcomes the deficiencies in the prior art, a kind of preparation method of 2-ethyl-4-methylimidazole is provided, adopts the method for fractional steps, namely complete ring-closure reaction with suitable catalyzer, dehydrogenation under active Raney's nickel catalyst exists again, adopts process for purification to obtain.Have by product few, pollute low, that yield is high, quality product is excellent feature.
To achieve these goals, technical scheme of the present invention is as follows:
A preparation method for 2-ethyl-4-methylimidazole, it comprises the steps:
By diamine and propionitrile in the presence of a catalyst, at 80 ~ 110 DEG C He at 120 ~ 140 DEG C, ring-closure reaction is carried out successively;
The product of described ring-closure reaction is carried out dehydrogenation reaction with Raney's nickel at 170 ~ 200 DEG C, obtains described 2-ethyl-4-methylimidazole.
Preferably, described catalyzer is sulfocompound.
Preferably, described sulfocompound is selected from the one in sulfur dichloride, tetra sulfur chloride, disulphur dichloride, elemental sulfur and thiophosphoric anhydride.Be preferably sulfur dichloride, tetra sulfur chloride, disulphur dichloride, because these three kinds of sulfocompounds are not all solids, are easily separated, avoid the process of conventional means zinc powder sulphur removal.
Preferably, the mol ratio of described diamine and propionitrile is (1 ~ 1.3): 1.
Preferably, described diamine is 1,2-propylene diamine.
Preferably, also comprise the step of the underpressure distillation of the product to described ring-closure reaction, in the step of described underpressure distillation, be collected in the product of azeotropic under 105 ~ 112 DEG C/15mmHg condition.
Preferably, also comprise the step of the product of described dehydrogenation reaction being carried out to underpressure distillation, in the step of described underpressure distillation, be collected in the product of azeotropic under 150 ~ 160 DEG C/10mmmHg condition.
Preferably, also comprise the step that described 2-ethyl-4-methylimidazole is refined: adding aqueous sodium hydroxide solution by 2-ethyl-4-methylimidazole, distill at 120 DEG C.
Preferably, the massfraction of described aqueous sodium hydroxide solution is 3%.
Preferably, the mass ratio of described 2-ethyl-4-methylimidazole and aqueous sodium hydroxide solution is 1:0.35.
The reaction process route that the inventive method relates to is as follows:
Therefore, the present invention compared with prior art, has the following advantages:
1. the present invention adopts the method for fractional steps to obtain 2-ethyl-4-methylimidazole, and process costs reduces, and optimizes reaction process, easy and simple to handle, and pollute and reduce, reaction yield is high;
2. ring-closure reaction of the present invention, select 1,2-propylene diamine and propionitrile are under agitation, liquid catalyst is adopted to complete condensation under certain temperature, obtained 2-ethyl-4-methylimidazole quinoline (hereinafter referred to as dihydro-compound), use fractionation plant in reaction, low-boiling-point substance is steamed in time, accelerate speed of response; In aftertreatment, catalyzer easily processes, and also can reuse after 1,2-excessive propylene diamine steams, greatly cost-saving;
3. dehydrogenation reaction of the present invention, use homemade Raney's nickel composite catalyst, catalyst activity is enhanced, and improves yield;
4. the present invention is by test of many times, takes certain method of purification, can obtain content and be greater than the more excellent 2-ethyl-4-methylimidazole of quality, meet the need of market.
Accompanying drawing explanation
By reading the detailed description done non-limiting example with reference to the following drawings, other features, objects and advantages of the present invention will become more obvious:
Fig. 1 is the nuclear magnetic spectrogram of 2-ethyl-4-methylimidazole prepared by the present invention;
Fig. 2 is the mass spectrum of 2-ethyl-4-methylimidazole prepared by the present invention.
Embodiment
According to following embodiment, the present invention may be better understood.But those skilled in the art will readily understand, concrete physics proportioning, processing condition and result thereof described by embodiment only for the present invention, and should can not limit the present invention described in claims yet.
Embodiment 1:
Ring-closure reaction: thermometer is housed at one, in the 1000ml there-necked flask of fractional column and prolong (attached electrically heated oil bath heating unit), add propionitrile 220 grams (4.0mol), sulfur dichloride 26 grams (0.2mol), under agitation add 1,2-propylene diamine 100 grams (1.35mol), due to exothermic heat of reaction, temperature rises.Under oil bath heating, under stirring, be warming up to 100 DEG C, react 3 hours at this temperature, then reduce pressure and the low-boiling-point substance in container steamed, add remaining 1,2-propylene diamine 226 grams (3.05mol) after having steamed again, continue heating, vigorous stirring, reacting liquid temperature rises to 130 DEG C, is incubated 1.5 hours at this temperature, and steams excessive 1,2-propylene diamine, reaction terminates.Reactant is chilled to room temperature, and the product of azeotropic part 105 ~ 112 DEG C/15mmHg is collected in underpressure distillation, can obtain dihydro-compound 390 grams, yield 87.1%.
Dehydrogenation reaction: dihydro-compound 550 grams is put into flask, open electric stirring, add Raney's nickel composite catalyst (Raney's nickel 22 grams to be added in the potassium hydroxide aqueous solution of 60mL20wt% and stir 15 minutes, obtain by pure water and Ethanol Treatment), oil bath is heated, be warming up to 190 DEG C under stirring, be incubated 3.5 hours.By static for reaction solution clarification, take out clear liquid, filter after adding a small amount of dilution with toluene in residuum, filtrate after filtering Raney's nickel and filtrate above merge, and carry out underpressure distillation, are first steamed by toluene in the pressure that shades, then the product of 150 ~ 160 DEG C/10mmmHg is collected, can obtain 2-ethyl-4-methylimidazole 488 grams, yield 90.4%, gas chromatographic analysis content is greater than 97%.
Refining: by 2-ethyl-4-methylimidazole 488 grams, to add the sodium hydroxide solution 170g of 3%, oil bath is heated, at being warming up to 120 DEG C under stirring, and insulation backflow 50 minutes.Underpressure distillation, collect the product of 154 DEG C ~ 157 DEG C/10mmmHg, can obtain light yellow smart finished product 452 grams, gas chromatographic analysis content is greater than 98.5%.
2-ethyl-4-methylimidazole prepared by the present embodiment is through nuclear-magnetism and mass spectrographic detection, and spectrogram is distinguished as depicted in figs. 1 and 2, wherein, in nuclear-magnetism spectrum,
1hNMR (CDCl
3) at 1.201ppm, 2.211ppm, 2.719ppm, 6.625ppm, 11.31ppm, there is characteristic peak respectively.
Embodiment 2:
At one, thermometer is housed, in the 1000ml there-necked flask of fractional column and prolong (attached electrically heated oil bath heating unit), add propionitrile 220 grams (4.0mol), chemistry bright sulfur 6.5 grams (0.2mol), under agitation add 1,2-propylene diamine 100 grams (1.35mol), due to exothermic heat of reaction, temperature rises.100 DEG C are warming up under stirring, react 3 hours at this temperature, then reducing pressure steams the moisture in container, adds remaining 1 again after having steamed, 2-propylene diamine 226 grams (3.05mol), continue heating, vigorous stirring, reacting liquid temperature rises to 130 DEG C, be incubated 1.5 hours at this temperature, and steaming 1,2-excessive propylene diamine, reaction terminates.Reaction product is chilled to room temperature, and the product of azeotropic part 105 ~ 112 DEG C/15mmHg is collected in underpressure distillation, can obtain dihydro-compound 320 grams, yield 71.4%.
Embodiment 3:
At one, thermometer is housed, in the 1000ml there-necked flask of fractional column and prolong (attached oil bath heating unit), add propionitrile 220 grams (4.0mol), thiophosphoric anhydride 44 grams (0.2mol), under agitation add 1,2-propylene diamine 100 grams (1.35mol), due to exothermic heat of reaction, temperature rises.100 DEG C are warming up under stirring, react 3 hours at this temperature, then reducing pressure steams the moisture in container, adds remaining 1 again after having steamed, 2-propylene diamine 226 grams (3.05mol), continue heating, vigorous stirring, reacting liquid temperature rises to 130 DEG C, be incubated 1.5 hours at this temperature, and steaming 1,2-excessive propylene diamine, reaction terminates substantially.Reaction product is chilled to room temperature, and the product of azeotropic part 105 ~ 112 DEG C/15mmHg is collected in underpressure distillation, can obtain dihydro-compound 360 grams, yield 80.3%.
Embodiment 4:
At one, thermometer is housed, in the 1000ml there-necked flask of fractional column and prolong (attached oil bath heating unit), add propionitrile 220 grams (4.0mol), tetra sulfur chloride 44 grams (0.2mol), under agitation add 1,2-propylene diamine 100 grams (1.35mol), due to exothermic heat of reaction, temperature rises.100 DEG C are warming up under stirring, react 3 hours at this temperature, then reducing pressure steams the moisture in container, adds remaining 1 again after having steamed, 2-propylene diamine 226 grams (3.05mol), continue heating, vigorous stirring, reacting liquid temperature rises to 130 DEG C, be incubated 1.5 hours at this temperature, and steaming 1,2-excessive propylene diamine, reaction terminates substantially.Reaction product is chilled to room temperature, and the product of azeotropic part 105 ~ 112 DEG C/15mmHg is collected in underpressure distillation, can obtain dihydro-compound 360 grams, yield 80.3%.
Embodiment 5:
At one, thermometer is housed, in the 1000ml there-necked flask of fractional column and prolong (attached electrically heated oil bath heating unit), add propionitrile 220 grams (4.0mol), disulphur dichloride 6.5 grams (0.2mol), under agitation add 1,2-propylene diamine 100 grams (1.35mol), due to exothermic heat of reaction, temperature rises.100 DEG C are warming up under stirring, react 3 hours at this temperature, then reducing pressure steams the moisture in container, adds remaining 1 again after having steamed, 2-propylene diamine 226 grams (3.05mol), continue heating, vigorous stirring, reacting liquid temperature rises to 130 DEG C, be incubated 1.5 hours at this temperature, and steaming 1,2-excessive propylene diamine, reaction terminates.Reaction product is chilled to room temperature, and the product of azeotropic part 105 ~ 112 DEG C/15mmHg is collected in underpressure distillation, can obtain dihydro-compound 320 grams, yield 71.4%.
Embodiment 6:
What obtain in embodiment 1 puts into flask by dihydro-compound 550 grams, opens electric stirring, adds Raney's nickel catalyst 15 grams, and oil bath is heated, and is warming up to 190 DEG C, is incubated 3.5 hours under stirring.By static for reaction solution clarification, take out clear liquid, filter after adding a small amount of dilution with toluene in residuum, filtrate after filtering Raney's nickel and filtrate above merge, and carry out underpressure distillation, are first steamed by toluene in the pressure that shades, then the product of 150 ~ 160 DEG C/10mmmHg is collected, can obtain 2-ethyl-4-methylimidazole 465 grams, yield 86.1%, gas chromatographic analysis content is greater than 97%.
Embodiment 7:
The dihydro-compound that embodiment 1 obtains 550 grams puts into flask, opens electric stirring, adds thunder Buddhist nun cobalt catalyst 15 grams, and oil bath is heated, and is warming up to 190 DEG C, is incubated 3.5 hours under stirring.By static for reaction solution clarification, take out clear liquid, filter after adding a small amount of dilution with toluene in residuum, filtrate after filtering Raney's nickel and filtrate above merge, and carry out underpressure distillation, are first steamed by toluene in the pressure that shades, then the product of 150 ~ 160 DEG C/10mmmHg is collected, can obtain 2-ethyl-4-methylimidazole 437 grams, yield 80.9%, gas chromatographic analysis content is greater than 97%.
Embodiment 8:
With the method for embodiment 1, difference is the ring-closure reaction the first step, and under oil bath heating, be warming up to 80 DEG C under stirring, react 5 hours at this temperature, then reducing pressure steams the low-boiling-point substance in container.
Embodiment 9:
With the method for embodiment 1, difference is the ring-closure reaction the first step, and under oil bath heating, be warming up to 110 DEG C under stirring, react 2.5 hours at this temperature, then reducing pressure steams the low-boiling-point substance in container.
Embodiment 10:
With the method for embodiment 1, difference is ring-closure reaction second step, and continue heating, vigorous stirring, reacting liquid temperature rises to 140 DEG C, is incubated 1 hour at this temperature, steams 1,2-excessive propylene diamine.
Embodiment 11:
With the method for embodiment 1, difference is ring-closure reaction second step, and continue heating, vigorous stirring to reacting liquid temperature rises to 120 DEG C, is incubated 3 hours at this temperature, steams 1,2-excessive propylene diamine.
Embodiment 12:
With the method for embodiment 1, in dehydrogenation reaction, dihydro-compound is put into flask, open electric stirring, add Raney's nickel composite catalyst, oil bath is heated, and is warming up to 170 DEG C, is incubated 5 hours under stirring.
With the method for embodiment 1, in dehydrogenation reaction, dihydro-compound is put into flask, open electric stirring, add Raney's nickel composite catalyst, oil bath is heated, and is warming up to 200 DEG C, is incubated 3 hours under stirring.
With the method for embodiment 1, FF, by 2-ethyl-4-methylimidazole, adds the sodium hydroxide solution of 3%, and oil bath is heated, at being warming up to 105 DEG C under stirring, and insulation backflow 65 minutes.
Embodiment 13:
With the method for embodiment 1, FF, by 2-ethyl-4-methylimidazole, adds the sodium hydroxide solution of 3%, and oil bath is heated, at being warming up to 130 DEG C under stirring, and insulation backflow 40 minutes.
With the method for embodiment 1, FF, crude product 2-ethyl-4-methylimidazole and 3% the mass ratio of sodium hydroxide solution be 1:0.25, oil bath is heated, at being warming up to 120 DEG C under stirring, insulation backflow 50 minutes.
With the method for embodiment 1, FF, crude product 2-ethyl-4-methylimidazole and 3% the mass ratio of sodium hydroxide solution be 1:0.45, oil bath is heated, at being warming up to 120 DEG C under stirring, insulation backflow 50 minutes.
Embodiment 14:
With the method for embodiment 1, difference is the reaction mol ratio of 1,2-propylene diamine and propionitrile is 1:1.
Embodiment 15:
With the method for embodiment 1, difference is the reaction mol ratio of 1,2-propylene diamine and propionitrile is 1.3:1.
In sum, be only preferred embodiment of the present invention, not be used for limiting scope of the invention process, all equalizations of doing according to shape, structure, feature and the spirit described in the claims in the present invention scope change and modify, and all should be included in right of the present invention.
Claims (10)
1. a preparation method for 2-ethyl-4-methylimidazole, is characterized in that, comprises the steps:
By diamine and propionitrile in the presence of a catalyst, at 80 ~ 110 DEG C He at 120 ~ 140 DEG C, ring-closure reaction is carried out successively;
The product of described ring-closure reaction is carried out dehydrogenation reaction with Raney's nickel at 170 ~ 200 DEG C, obtains described 2-ethyl-4-methylimidazole.
2. prepare the method for 2-ethyl-4-methylimidazole as claimed in claim 1, it is characterized in that, described catalyzer is sulfocompound.
3. prepare the method for 2-ethyl-4-methylimidazole as claimed in claim 2, it is characterized in that, described sulfocompound is selected from the one in sulfur dichloride, tetra sulfur chloride, disulphur dichloride, elemental sulfur and thiophosphoric anhydride.
4. prepare the method for 2-ethyl-4-methylimidazole as claimed in claim 1, it is characterized in that, the mol ratio of described diamine and propionitrile is (1 ~ 1.3): 1.
5. the method preparing 2-ethyl-4-methylimidazole as described in claim 1 or 4, is characterized in that, described diamine is 1,2-propylene diamine.
6. prepare the method for 2-ethyl-4-methylimidazole as claimed in claim 1, it is characterized in that, also comprise the step of the underpressure distillation of the product to described ring-closure reaction, in the step of described underpressure distillation, be collected in the product of azeotropic under 105 ~ 112 DEG C/15mmHg condition.
7. prepare the method for 2-ethyl-4-methylimidazole as claimed in claim 1, it is characterized in that, also comprise the step of the product of described dehydrogenation reaction being carried out to underpressure distillation, in the step of described underpressure distillation, be collected in the product of azeotropic under 150 ~ 160 DEG C/10mmmHg condition.
8. prepare the method for 2-ethyl-4-methylimidazole as claimed in claim 1, it is characterized in that, also comprise the step that described 2-ethyl-4-methylimidazole is refined: adding aqueous sodium hydroxide solution by 2-ethyl-4-methylimidazole, distill at 120 DEG C.
9. prepare the method for 2-ethyl-4-methylimidazole as claimed in claim 8, it is characterized in that, the massfraction of described aqueous sodium hydroxide solution is 3%.
10. prepare the method for 2-ethyl-4-methylimidazole as claimed in claim 9, it is characterized in that, the mass ratio of described 2-ethyl-4-methylimidazole and aqueous sodium hydroxide solution is 1:0.35.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110845415A (en) * | 2019-11-07 | 2020-02-28 | 广州市固研电子材料有限公司 | Environment-friendly synthesis method of 2-ethyl-4-methylimidazole |
| CN113004204A (en) * | 2021-03-25 | 2021-06-22 | 湖北江大化工股份有限公司 | Preparation method of 2-undecylimidazoline |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2512513A1 (en) * | 1975-03-21 | 1976-10-07 | Basf Ag | 2-Imidazoline cpds. prepn. - by reacting 1,2-diamines with nitriles in the presence of polysulphide salts |
| US4340744A (en) * | 1980-03-13 | 1982-07-20 | Basf Aktiengesellschaft | Preparation of imidazoles |
-
2015
- 2015-12-24 CN CN201510982506.1A patent/CN105367499A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2512513A1 (en) * | 1975-03-21 | 1976-10-07 | Basf Ag | 2-Imidazoline cpds. prepn. - by reacting 1,2-diamines with nitriles in the presence of polysulphide salts |
| US4340744A (en) * | 1980-03-13 | 1982-07-20 | Basf Aktiengesellschaft | Preparation of imidazoles |
Non-Patent Citations (3)
| Title |
|---|
| 天津化工研究所: "2-乙基-4-甲基咪唑", 《塑料工业》 * |
| 王晓川等: "1-氨丙基-2-甲基咪唑的合成及表征", 《广东化工》 * |
| 郑雯等: "1-氨丙基-2-甲基咪唑的合成与表征", 《精细化工》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110845415A (en) * | 2019-11-07 | 2020-02-28 | 广州市固研电子材料有限公司 | Environment-friendly synthesis method of 2-ethyl-4-methylimidazole |
| CN110845415B (en) * | 2019-11-07 | 2022-12-16 | 广东固研电子材料有限公司 | Environment-friendly synthesis method of 2-ethyl-4-methylimidazole |
| CN113004204A (en) * | 2021-03-25 | 2021-06-22 | 湖北江大化工股份有限公司 | Preparation method of 2-undecylimidazoline |
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Application publication date: 20160302 |