CN1424314A - Clean eoxidation of alpha-beta-unsaturated carbonyl compound - Google Patents
Clean eoxidation of alpha-beta-unsaturated carbonyl compound Download PDFInfo
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- CN1424314A CN1424314A CN 02159873 CN02159873A CN1424314A CN 1424314 A CN1424314 A CN 1424314A CN 02159873 CN02159873 CN 02159873 CN 02159873 A CN02159873 A CN 02159873A CN 1424314 A CN1424314 A CN 1424314A
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Abstract
A clean process for epoxidizing alpha, beta-unsaturated carbonyl compound features that the ionic liquid prepared from the cations of alkylpyridine or 1,3-dialkyl imidazole and the inorganic or organic anions, and the aqueous solution constitute a double-phase system, and under alkaline condition, the hydrogen peroxide as oxidant and said alpha, beta-unsaturated carbonyl compound take part in epoxidizing reaction. Its advantages are no need of organic solvent, high conversion rate and selectivity, high purity of product and cyclic use of ionic liquid.
Description
Technical field
The ionic liquid that the present invention relates to a kind of high-efficiency cleaning is as reaction medium and catalyst α, beta-unsaturated carbonyl compound epoxidizing method.
Technical background
The ketenes epoxidation is very important organic synthesis, and the chemical intermediate organic epoxide of its preparation is widely used in fields such as macromolecular material, medicine, printing and dyeing.For sterically hindered bigger α, beta-unsaturated carbonyl compound, traditional transition metal and phase transfer catalytic technology (PTC) though etc. the epoxidation reaction of this compounds of research obtained some achievements, but these method ubiquities that reaction conditions requires that harsh (＜0 ℃ and titration reinforced), efficient are low, transformation efficiency and selectivity is not ideal enough, the easy open loop of epoxy compounds and use problem such as inflammable poisonous organic solvent under the alkaline condition.Exploitation low toxicity, α efficiently, the beta-unsaturated carbonyl compound epoxidizing method not only has important economic benefit, but also has good benefits in environment.
In recent years, eco-friendly catalyst system provided more wide space to ionic liquid at room temperature for people explore.Room-temperature ion liquid itself has excellent chemistry and thermodynamic stability, many materials all there is good solvency power, and at room temperature there is vapour pressure hardly, partial ion liquid has minimum water-soluble, and this makes it be applied in to have concurrently in the catalyzed reaction and be convenient to that product separates and the characteristic of catalyst recovery.At present, various countries scholar and researchist have realized much having the catalyzed reaction of important economic worth effectively in ionic liquid.
Summary of the invention
The objective of the invention is to replace ketenes epoxidizing method in traditional phase transfer catalysis system, a kind of efficient and eco-friendly reaction medium and catalyzer are provided, under mild reaction conditions, catalysis α, beta-unsaturated carbonyl compound epoxidation reaction.
Method of the present invention, it is characterized in that using nitrogen-containing heterocycle compound positively charged ion and ionic liquid inorganic or that organic anion constitutes to be reaction medium and catalyzer, under normal temperature and pressure and alkaline condition, hydrogen peroxide is an oxygenant, 10 to 200 minutes reaction times, catalysis α, the beta-unsaturated carbonyl compound epoxidation reaction.
Nitrogen-containing heterocycle compound positively charged ion of the present invention and ionic liquid reaction medium and catalyzer inorganic or that organic anion constitutes is characterized in that the nitrogen-containing heterocycle compound positively charged ion is alkyl pyridine or 1, and 3-dialkylimidazolium positively charged ion, alkyl chain length are C
1To C
6
Nitrogen-containing heterocycle compound positively charged ion of the present invention and ionic liquid reaction medium and catalyzer inorganic or that organic anion constitutes is characterized in that inorganic or organic anion is that tetrafluoro closes borate, hexafluoro closes phosphate radical, chlorine aluminate, trifluoracetic acid root, acetate, nitrate radical, nitrite anions, tosic acid root, Phenylsulfonic acid root, trifluoromethanesulfonic acid root, sulfate radical, perchlorate, chlorion, bromide anion, iodide ion.
Method of the present invention is characterized in that employed reactant α, and beta-unsaturated carbonyl compound is methyl pentenone, benzylideneacetone, cinnamophenone, isophorone, cyclonene, Karvon, α-Nai Kun, methyl cinnamate.
Under the alkaline condition of the present invention, the alkali of adding is yellow soda ash, salt of wormwood, sodium bicarbonate, sodium hydroxide.
Method of the present invention is characterized in that α, and the pH value of beta-unsaturated carbonyl compound epoxidation reaction system is 8 to 14.
Method of the present invention is characterized in that α, and the mol ratio of beta-unsaturated carbonyl compound and hydrogen peroxide is 1: 1 to 1: 10.
The present invention realizes by following measure:
Ion liquid typical production used in the present invention is: get equimolar bromination 1, after 3-dialkylimidazolium salt and ammonium hexafluorophosphate mix, normal temperature stirred 24 hours down in proper amount of acetone, remove insoluble solid, steam and remove acetone, kept 1 to 3 hour under 80 ℃ of vacuum, promptly obtain a kind of limpid liquid that at room temperature is in a liquid state, be phosphofluoric acid 1,3-dialkylimidazolium ionic liquid at room temperature.Ion liquid synthesizing of other kind can be with reference to reference (Huddleston J G, Visser A E, Reichert W M, Willauer H D, Broker G A, Rogers R D, Green Chem.2001,3,156).
The process of this epoxidation reaction is: in the round-bottomed flask of magnetic stirring apparatus is housed, add ionic liquid, α successively, beta-unsaturated carbonyl compound, aqueous hydrogen peroxide solution and alkaline solution.Wherein, α, the mol ratio of beta-unsaturated carbonyl compound and hydrogen peroxide is 1: 1 to 1: 10, transferring system pH with alkaline solution is 8 to 14.Stir stopped reaction after 10 to 200 minutes then at normal temperatures and pressures.Because the aqueous solution and ionic liquid do not dissolve each other, with the ionic liquid natural layering.Pour toluene into and fully extract, tell the superiors' organic phase, use the HP1790 gas chromatograph to carry out qualitative and quantitative analysis.Concentrate organic phase, decompression steams product.Tell lower floor's ionic liquid phase, vacuumize 30 minutes purifying under in 80 to 100 ℃ after, can reuse.
The present invention compares its substantial characteristics with traditional phase-transfer catalysis epoxidation process synthesizing epoxy compound:
1. reaction conditions gentleness (room temperature), experimental implementation is easy, has reduced energy consumption;
2. conventional organic solvents is not used in reaction, is an eco-friendly process;
3. have higher substrate conversion efficiency and selectivity of product;
4. the ionic liquid that reacted vacuumizes under 80 to 100 ℃ and handled several minutes, can reuse.
Embodiment embodiment 1: the epoxidation reaction of methyl pentenone in ionic liquid/water biphasic catalysis system (comparing with organic solvent/water transfer catalysis method)
Get phosphofluoric acid 1-methyl-3-butyl imidazole ([BMIm] PF
6) ionic liquid 15mL, adding the 0.044mol methyl pentenone successively, 25mL aqueous hydrogen peroxide solution (30%) and 8.7mL aqueous sodium hydroxide solution (1M) are in the stopped reaction after 150 minutes of stirring reaction under the room temperature.After pouring toluene into and fully extracting, use the HP1790 gas chromatograph to carry out qualitative and quantitative analysis.
Simultaneously, replace ionic liquid with isopyknic organic solvent dichloromethane, add 0.009mol Tetrabutylammonium bromide (TBAB) and benzyl trimethyl ammonium chloride (BTMAC) respectively as catalyzer, under equal conditions reaction is analyzed after the solvent extraction.Concrete reaction result is listed in table 1.The epoxidation reaction of methyl pentenone in table 1. ionic liquid/water biphasic catalysis system (comparing) with organic solvent/water transfer catalysis method
Embodiment 2: the epoxidation reaction of cyclonene in ionic liquid/water biphasic catalysis system (comparing with organic solvent/water transfer catalysis method)
| Catalyst system | Catalyzer | Methyl pentenone transformation efficiency (%) | Epoxide selectivity (%) |
| ??[BMIm]PF 6/ water | ??—— | ??????100 | ??????99 |
| ??CH 2Cl 2/ water | ??TBAB | ??????7 | ??????85 |
| ??CH 2Cl 2/ water | ??BTMAC | ??????20 | ??????84 |
Replace the 0.044mol methyl pentenone with the 0.044mol cyclonene, all the other are with embodiment 1.Reaction result is listed in table 2.The epoxidation reaction of cyclonene in table 2. ionic liquid/water biphasic catalysis system (comparing) with organic solvent/water transfer catalysis method
Embodiment 3: methyl pentenone epoxidation reaction performance relatively in different ionic liquid/water biphasic catalysis system
| Catalyst system | Catalyzer | Cyclonene transformation efficiency (%) | Epoxide selectivity (%) |
| ??[BMIm]PF 6/ water | ??—— | ??????92 | ??????99 |
| ??CH 2Cl 2/ water | ??TBAB | ??????5 | ??????76 |
| ??CH 2Cl 2/ water | ??BTMAC | ??????15 | ??????81 |
Use phosphofluoric acid 1-methyl-3-propyl imidazole ([C respectively
3MIm] PF
6), phosphofluoric acid 1-methyl-3-amyl group imidazoles ([C
5MIm] PF
6), phosphofluoric acid 1-methyl-3-hexyl imidazoles ([C
6MIm] PF
6) replacement phosphofluoric acid 1-methyl-3-butyl imidazole ([BMIm] PF
6), all the other are with embodiment 1.Reaction result is listed in table 3.The epoxidation reaction performance of methyl pentenone relatively in table 3. different ionic liquid/water biphasic catalysis system
Embodiment 4: methyl pentenone epoxidation reaction intermediate ion liquid repeat performance
| Catalyst system | Methyl pentenone transformation efficiency (%) | Epoxide selectivity (%) |
| ????[C 3MIm]PF 6/ water | ????100 | ????97 |
| ????[C 5MIm]PF 6/ water | ????99 | ????99 |
| ????[C 6MIm]PF 6/ water | ????96 | ????99 |
Ionic liquid reaction back among the embodiment 1 was 100 ℃ of following underpressure distillation 15 minutes, and the reinforced once more epoxidation reaction that repeats circulates nine times, the results are shown in table 4.Table 4. ionic liquid/water biphasic catalysis system intermediate ion liquid is to the repeated use result of methyl pentenone epoxidation reaction
| Cycle index | 1 | ?2 | ?3 | ?4 | ?5 | ?6 | ?7 | ?8 | ?9 |
| Methyl pentenone transformation efficiency (%) | 100 | ?99 | ?100 | ?100 | ?98 | ?99 | ?100 | ?99 | ?98 |
| Epoxide selectivity (%) | 99 | ?100 | ?100 | ?98 | ?99 | ?97 | ?98 | ?98 | ?97 |
Claims (7)
1. the α of a cleaning, the beta-unsaturated carbonyl compound epoxidizing method, it is characterized in that using nitrogen-containing heterocycle compound positively charged ion and ionic liquid inorganic or that organic anion constitutes to be catalyzer and reaction medium, under normal temperature and pressure and the alkaline condition, hydrogen peroxide is an oxygenant, reaction times is 10 to 200 minutes, catalysis α, and the beta-unsaturated carbonyl compound epoxidation reaction is produced corresponding epoxy compounds.
2. the method for claim 1 is characterized in that the nitrogen-containing heterocycle compound positively charged ion is alkyl pyridine or 1, the 3-dialkylimidazolium, and alkyl chain length is C
1To C
6
3. the method for claim 1 is characterized in that inorganic or organic anion is that tetrafluoro closes borate, hexafluoro closes phosphate radical, chlorine aluminate, trifluoracetic acid root, acetate, nitrate radical, nitrite anions, tosic acid root, Phenylsulfonic acid root, trifluoromethanesulfonic acid root, sulfate radical, perchlorate, chlorion, bromide anion, iodide ion.
4. the method for claim 1 is characterized in that employed reactant α, and beta-unsaturated carbonyl compound is methyl pentenone, benzylideneacetone, cinnamophenone, isophorone, cyclonene, Karvon, α-Nai Kun, methyl cinnamate.
5. the method for claim 1 is characterized in that employed alkali is yellow soda ash, salt of wormwood, sodium bicarbonate, sodium hydroxide.
6. method as claimed in claim 5 is characterized in that α, and the pH value of beta-unsaturated carbonyl compound epoxidation reaction system is 8 to 14.
7. the method for claim 1 is characterized in that α, and the mol ratio of beta-unsaturated carbonyl compound and hydrogen peroxide is 1: 1 to 1: 10.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021598738A CN1184217C (en) | 2002-12-24 | 2002-12-24 | Clean eoxidation of alpha-beta-unsaturated carbonyl compound |
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| CNB021598738A CN1184217C (en) | 2002-12-24 | 2002-12-24 | Clean eoxidation of alpha-beta-unsaturated carbonyl compound |
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| CN1184217C CN1184217C (en) | 2005-01-12 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101824069A (en) * | 2010-03-08 | 2010-09-08 | 浙江工业大学 | Method for preparing 4,5-epoxy-17beta-hydroxyl-androstane-3-ketone |
| CN102285945A (en) * | 2011-06-27 | 2011-12-21 | 中国人民大学 | Method for preparing alpha-carbonyl epoxy compound |
| CN104262295A (en) * | 2014-08-29 | 2015-01-07 | 浙江工业大学 | Synthesis method of epoxy chalcone and derivatives thereof |
| CN104974093A (en) * | 2015-06-17 | 2015-10-14 | 武汉海斯普林科技发展有限公司 | Imidazolium ionic liquid, application thereof and preparation method of 2, 5-azodicarboxylic acid diethyl ester-3, 4-ethylenedioxythiophene |
| CN113321287A (en) * | 2021-06-09 | 2021-08-31 | 昆明理工大学 | Method for degrading antibiotics by hydrogen peroxide through ionic liquid aqueous phase transfer catalysis |
| CN114149389A (en) * | 2022-01-13 | 2022-03-08 | 万华化学集团股份有限公司 | Preparation method of naphthoquinone epoxy compound |
| CN115093315A (en) * | 2022-07-07 | 2022-09-23 | 云南民族大学 | Synthesis method of 2-benzylidene-3-cyclohexenone compound |
-
2002
- 2002-12-24 CN CNB021598738A patent/CN1184217C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101824069A (en) * | 2010-03-08 | 2010-09-08 | 浙江工业大学 | Method for preparing 4,5-epoxy-17beta-hydroxyl-androstane-3-ketone |
| CN101824069B (en) * | 2010-03-08 | 2012-06-27 | 浙江工业大学 | Method for preparing 4,5-epoxy-17beta-hydroxyl-androstane-3-ketone |
| CN102285945A (en) * | 2011-06-27 | 2011-12-21 | 中国人民大学 | Method for preparing alpha-carbonyl epoxy compound |
| CN104262295A (en) * | 2014-08-29 | 2015-01-07 | 浙江工业大学 | Synthesis method of epoxy chalcone and derivatives thereof |
| CN104262295B (en) * | 2014-08-29 | 2016-05-11 | 浙江工业大学 | The synthetic method of a kind of epoxy chalcone and derivative thereof |
| CN104974093A (en) * | 2015-06-17 | 2015-10-14 | 武汉海斯普林科技发展有限公司 | Imidazolium ionic liquid, application thereof and preparation method of 2, 5-azodicarboxylic acid diethyl ester-3, 4-ethylenedioxythiophene |
| CN113321287A (en) * | 2021-06-09 | 2021-08-31 | 昆明理工大学 | Method for degrading antibiotics by hydrogen peroxide through ionic liquid aqueous phase transfer catalysis |
| CN114149389A (en) * | 2022-01-13 | 2022-03-08 | 万华化学集团股份有限公司 | Preparation method of naphthoquinone epoxy compound |
| CN114149389B (en) * | 2022-01-13 | 2023-09-19 | 万华化学集团股份有限公司 | Preparation method of naphthoquinone epoxy compound |
| CN115093315A (en) * | 2022-07-07 | 2022-09-23 | 云南民族大学 | Synthesis method of 2-benzylidene-3-cyclohexenone compound |
| CN115093315B (en) * | 2022-07-07 | 2024-04-26 | 云南民族大学 | Synthesis method of 2-benzylidene-3-cyclohexenone compound |
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| Publication number | Publication date |
|---|---|
| CN1184217C (en) | 2005-01-12 |
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