CN1425657A - Olefine epoxidation method in ionic liquid - Google Patents
Olefine epoxidation method in ionic liquid Download PDFInfo
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- CN1425657A CN1425657A CN 02160381 CN02160381A CN1425657A CN 1425657 A CN1425657 A CN 1425657A CN 02160381 CN02160381 CN 02160381 CN 02160381 A CN02160381 A CN 02160381A CN 1425657 A CN1425657 A CN 1425657A
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- ionic liquid
- porphyrin
- phenyl
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Abstract
The present invention relates to one olefin epoxidation process is mixed ionic liquid-organic solvent system and with metal prophyrin as catalyst. The ionic liquid consists of dialkyl imidazole cation and acid radical anion. After the reaction, the product is extracted with organic solvent and the catalyst is left in the ion liquid for reuse. The said process can separate catalyst and product in the homogeneous reaction system, and has fast reaction speed, high substrate converting rate and high epoxidized product selectivity.
Description
Technical field
The present invention relates to olefin epoxidation method in a kind of ionic liquid.
Background technology
Epoxy compounds is the important organic oxygen-containing compound of a class, is normally prepared by Sauerstoffatom and combining of alkene.Natural product and some aromatic hydrocarbon have the bio-oxidation product of carinogenicity, are exactly epoxy compounds.It still is the important synthetic intermediate of many organic compound, can change into a series of staple products.Because there are many drawbacks in traditional preparation method, so the epoxidation process of alkene was both very important under the development mild conditions, have to have potential society, economic benefit, become the very interested research field of chemist.The cytochrome P 450 monooxygenases of occurring in nature can be realized the oxygenation reaction of hydro carbons under mild conditions, the active centre of enzyme is an iron porphyrin, and from the late nineteen seventies early eighties, because the develop rapidly of homogeneous catalysis oxidizing reaction, based on to realizing the needs of the functional response that cytochrome P-450 had under the mild conditions in the understanding of metalloporphyrin oxygenizement in enzyme system and science and the applied research, begun the big quantity research of metalloporphyrin as potential catalyst for oxidation reaction and enzyme model.(1992, (92): introduced metalloporphyrin in one piece of summary 1411) is the effective catalyst of catalyzed oxidation hydro carbons and oxidation scission DNA to B.Meunier at Chem.Rev..
But the employed catalyzer price of homogeneous system height, the difficult separation and recycling of catalyzer, and metalloporphyrin easy oxidized destruction in strong well-oxygenated environment are big defectives in present this field.In a large number with an organic solvent, easily cause environmental pollution in the while homogeneous reaction.In recent years, a kind of emerging green solvent---ionic liquid at room temperature has become the focus of research.Ionic liquid does not almost have vapour pressure, can dissolve many organic and inorganicss, is easy to and other separating substances, can recycle etc. good characteristic, make it in organic synthesis, potentiality have a wide range of applications in the fields such as catalyzed reaction.
Summary of the invention
The objective of the invention is to overcome the shortcoming that above-mentioned epoxidation reaction exists, a kind of olefin epoxidation method is provided, and this method uses ionic liquid at room temperature to make solvent, and environmental pollution is little, can isolate product from reaction mixture easily, catalyzer can be reused simultaneously.
The method of epoxidation reaction of olefines method in a kind of ionic liquid; the ionic liquid that it is characterized in that using the positively charged ion that contains quaternary nitrogen and acid radical anion to constitute is reaction medium; with the metalloporphyrin title complex is catalyzer; at normal temperatures; iodosobenzene and diacetyl iodobenzene are oxygenant, carry out EPOXIDATION OF ALKENES CATALYZED BY.
Ionic liquid of the present invention is by dialkylimidazolium positively charged ion and hexafluoro-phosphate radical PF
6 -Form, molecular formula can be expressed as [C
nMim] PF
6, [C wherein
nMim] be 1-alkyl-3-Methylimidazole positively charged ion, alkyl chain length is C
1To C
6This ionic liquid is stable to empty G﹠W, has the liquid scope of non-constant width, and catalyzer is had good solvability.
Catalyzer of the present invention is the metalloporphyrin title complex, and its central metal can be Mn, Fe, Co, Mo or Cu, the porphyrin part is TPP (5,10,15, the 20-tetraphenylporphyrin), TMP (5,10,15,20-four-(2,4, the 6-trimethylammonium) phenyl) porphyrin), TMOPP (5,10,15,20-four-(right-methoxyl group) phenyl) porphyrin), TDCPP (5,10,15,20-four-(2, the 6-dichloro) phenyl) porphyrin), TDCPPBr
8(5,10,15,20-four-(2, the 6-dichloro) phenyl-Beta-bromo) porphyrin) or TFPP (5,10,15,20-four-(phenyl-pentafluoride base) porphyrin).
Method of the present invention is characterized in that employed alkene can be vinylbenzene, substituted phenylethylene, cyclic aliphatic alkene, atomatic olefins and normal olefine.
Method of the present invention is characterized in that ionic liquid and volume of organic solvent ratio are 1: 2 to 10: 1.
Method of the present invention, the mol ratio that it is characterized in that catalyzer and substrate alkene is 1: 25 to 1: 150.
The present invention realizes by following measure:
Ion liquid typical production used in the present invention is: get equimolar bromination 1,3-dialkylimidazolium salt and ammonium hexafluorophosphate are dissolved in the appropriate amount of deionized water, normal temperature stirred 24 hours down, remove insoluble solid, go out ionic liquid with dichloromethane extraction, rotation is steamed and is removed methylene dichloride, kept 1 to 3 hour under 80 ℃ of vacuum, promptly obtain a kind ofly at room temperature being in a liquid state phosphofluoric acid 1,3-dialkylimidazolium ionic liquid at room temperature.
The process of epoxidation reaction is: in 7 milliliters of volumetrical bottles, add ionic liquid, catalysis of metalloporphyrin agent, substrate alkene, methylene dichloride and oxygenant successively.Wherein, the mol ratio of catalyzer and substrate is 1: 25 to 1: 150, stopped reaction after 20 ℃ of normal temperature stir 1 hour down.With going out product, use the HP5890 gas chromatograph to carry out qualitative and quantitative analysis with immiscible normal hexane of ionic liquid or extracted with diethyl ether.Because catalyzer is still stayed in the ionic liquid, therefore can recycle.
In order further to set forth the present invention, the spy provides following examples.
Embodiment embodiment 1: cinnamic epoxidation
The MnTFPPCl of 2 μ mol is dissolved in phosphofluoric acid 1-methyl-3-butyl imidazole ([bmim] PF of 1.5ml
6) in the ionic liquid, add 200 μ mol vinylbenzene, add 1ml CH again
2Cl
2, add 200 μ mol diacetyl iodobenzenes under stirring, 20 ℃ were reacted 1 hour, after epoxidation reaction finishes, with n-hexane extraction place product and the intact raw material of unreacted.Be dissolved with in the ionic liquid of catalyzer and add vinylbenzene again, CH
2Cl
2With the diacetyl iodobenzene; the same terms is reaction down; circulate 5 times, reaction result is as shown in the table: catalyst recirculation number of times styrene conversion rate % Styryl oxide yield % raw catalyst 86 86
1 88 87
2 89 88
3 91 90
4 91 90
5 91 90 embodiment 2: cinnamic epoxidation
The FeTFPPCl of 2 μ mol is dissolved in phosphofluoric acid 1-methyl-3-butyl imidazole ([bmim] PF of 1.5ml
6) in the ionic liquid, add 50 μ mol vinylbenzene, add 0.5ml CH again
2Cl
2, add 100 μ mol diacetyl iodobenzenes under stirring, 20 ℃ were reacted 1 hour, and the styrene conversion rate is 99%, and epoxidation of styrene thing yield is 93%.Embodiment 3: the epoxidation of cyclooctene
The MnTPPCl of 2 μ mol is dissolved in phosphofluoric acid 1-methyl-3-butyl imidazole ([bmim] PF of 1.5ml
6) in the ionic liquid, add 100 μ mol cyclooctene, add 0.5ml CH again
2Cl
2, add 50 μ mol iodosobenzenes under stirring, 20 ℃ were reacted 1 hour, and the cyclooctene transformation efficiency is 98%, and oxirane ring octane yield is 90%.The epoxidation of embodiment 4:1-ten alkene
The MnTFPPCl of 2 μ mol is dissolved in phosphofluoric acid 1-methyl-3-butyl imidazole ([bmim] PF of 1.5ml
6) in the ionic liquid, add 300 μ mol 1-, ten alkene, add 1ml CH again
2Cl
2, add 450 μ mol diacetyl iodobenzenes under stirring, 20 ℃ were reacted 1 hour, and 1-ten alkene transformation efficiencys are 97.9%, 1, and 2-epoxy ten alkane yields are 95%.Embodiment 5:1, the epoxidation of 2-dialin
The FeTPP of 2 μ mol is dissolved in phosphofluoric acid 1-methyl-3-ethyl imidazol(e) ([emim] PF of 1.5ml
6) in the ionic liquid, adding 300 μ mol 1, the 2-dialin adds 1mlCH again
2Cl
2, add 450 μ mol diacetyl iodobenzenes under stirring, 20 ℃ were reacted 1 hour, and 1,2-dialin transformation efficiency is 97%, the epoxidation product yield is 91%.Embodiment 6: the epoxidation of cis-stilbene
The CoTPP of 2 μ mol is dissolved in phosphofluoric acid 1-methyl-3-ethyl imidazol(e) ([emim] PF of 1.5ml
6) in the ionic liquid, add 300 μ mol cis-stilbene, add 1ml CH again
2Cl
2, add 450 μ mol diacetyl iodobenzenes under stirring, 20 ℃ were reacted 1 hour, and cis-stilbene transformation efficiency is 88%, and the epoxidation product yield is 85%.
Claims (6)
1. epoxidation reaction of olefines method in the ionic liquid; the ionic liquid that it is characterized in that using the positively charged ion that contains quaternary nitrogen and acid radical anion to constitute is reaction medium; with the metalloporphyrin title complex is catalyzer; at normal temperatures; iodosobenzene and diacetyl iodobenzene are oxygenant, carry out EPOXIDATION OF ALKENES CATALYZED BY.
2. by the method for claim 1, it is characterized in that ionic liquid is by dialkylimidazolium positively charged ion and hexafluoro-phosphate radical PF
6 -Form, molecular formula is expressed as [C
nMim] PF
6, [C wherein
nMim] be 1-alkyl-3-Methylimidazole positively charged ion, alkyl chain length is C
1To C
6
3. by the method for claim 1, it is characterized in that the metalloporphyrin title complex, its central metal can be Mn, Fe, Co, Mo or Cu, porphyrin part are TPP (5,10,15, the 20-tetraphenylporphyrin), TMP (5,10,15,20-four-(2,4, the 6-trimethylammonium) phenyl) porphyrin), TMOPP (5,10,15,20-four-(right-methoxyl group) phenyl) porphyrin), TDCPP (5,10,15,20-four-(2, the 6-dichloro) phenyl) porphyrin), TDCPPBr
8(5,10,15,20-four-(2, the 6-dichloro) phenyl-Beta-bromo) porphyrin) or TFPP (5,10,15,20-four-(phenyl-pentafluoride base) porphyrin).
4. by the method for claim 1, it is characterized in that alkene can be vinylbenzene, substituted phenylethylene, cyclic aliphatic alkene, atomatic olefins and normal olefine.
5. by the method for claim 1, it is characterized in that ionic liquid and volume of organic solvent ratio are 1: 2 to 10: 1.
6. by the method for claim 1, the mol ratio that it is characterized in that catalyzer and substrate alkene is 1: 25 to 1: 150.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02160381 CN1425657A (en) | 2002-12-30 | 2002-12-30 | Olefine epoxidation method in ionic liquid |
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|---|---|---|---|
| CN 02160381 CN1425657A (en) | 2002-12-30 | 2002-12-30 | Olefine epoxidation method in ionic liquid |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100345608C (en) * | 2004-06-22 | 2007-10-31 | 中国科学院过程工程研究所 | Organic substance extraction in water with ionic liquid as extractant |
| CN101735174B (en) * | 2009-12-09 | 2012-12-05 | 辽宁大学 | Homogeneous catalytic olefin epoxidation method for dissipated metal rhenium ionic liquid |
| CN107753947A (en) * | 2017-11-10 | 2018-03-06 | 中国人民解放军第四军医大学 | A kind of glyoxaline ion liquid type sensitising agent and its preparation method and application |
-
2002
- 2002-12-30 CN CN 02160381 patent/CN1425657A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100345608C (en) * | 2004-06-22 | 2007-10-31 | 中国科学院过程工程研究所 | Organic substance extraction in water with ionic liquid as extractant |
| CN101735174B (en) * | 2009-12-09 | 2012-12-05 | 辽宁大学 | Homogeneous catalytic olefin epoxidation method for dissipated metal rhenium ionic liquid |
| CN107753947A (en) * | 2017-11-10 | 2018-03-06 | 中国人民解放军第四军医大学 | A kind of glyoxaline ion liquid type sensitising agent and its preparation method and application |
| CN107753947B (en) * | 2017-11-10 | 2020-04-28 | 中国人民解放军第四军医大学 | Imidazole ionic liquid photosensitizer and preparation method and application thereof |
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