CN101109016A - Method of zyme catalyzing cyclo-olefin oxidation - Google Patents
Method of zyme catalyzing cyclo-olefin oxidation Download PDFInfo
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- CN101109016A CN101109016A CNA2006100472559A CN200610047255A CN101109016A CN 101109016 A CN101109016 A CN 101109016A CN A2006100472559 A CNA2006100472559 A CN A2006100472559A CN 200610047255 A CN200610047255 A CN 200610047255A CN 101109016 A CN101109016 A CN 101109016A
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Abstract
The invention relates to a method of enzyme catalyzing olefin expoxidation. In the aqueous solution, the bromine peroxidase is applied for biological catalyst and hydrogen peroxide or oxygen is taken as oxygen source to oxidate the olefin into expoxidation. Take the cyclohexen as example. The hydrogen peroxide is applied as the source. They react under the 20 DEG C. to 70 DEG C. for two to ten hours. The yield of epoxy cyclohexane to the hydrogen peroxide is more than 50 per cent and the selectivity of the epoxy cyclohexane is more than 85 per cent. After the reaction, the water phase is separated from the organic phase automatically, and the enzymes left in the water phase can be recycled. Boasting easy technical process, recycled enzymes and easy yield separation, the method is an environment-friendly green chemical process.
Description
Technical field
The present invention relates to method of zyme catalyzing cyclo-olefin oxidation, specifically a kind of method (generating epoxy cyclohexane) of using the bromine peroxide enzyme catalyzing expoxidation of olefines as tetrahydrobenzene.
Background technology
Epoxy compounds is the very useful synthetic intermediate of a class, is widely used in petrochemical complex, fine chemistry industry and organic synthesis.But up to now, the main method of industrial production epoxy compounds is a chemical method: comprise halogenohydrin method, Halcon method, domestic then based on the halogenohydrin method, there is severe environmental pollution in these methods or the problem of joint product are arranged.In the chemical catalysis synthesizing epoxy compound catalyzer heavy metal being arranged, is the potential environomental pollution source, and most of processes have patent protection in addition, invest greatly (Science, 2001,292:1139-1141).Utilizing the enzyme catalysis alkene epoxidation is a very promising route of synthesis, the particularly develop rapidly of Protocols in Molecular Biology in recent years, the mass-produced technology of enzyme is more and more ripe, cost is more and more lower, can satisfy the required enzyme amount of large-scale commercial production, therefore carry out alkene epoxidation synthetic ripe (Science on opportunity with biological catalysis, 2003,299:1694-1697).Bromine peroxide enzyme is applied to the existing report of oxidation of organosulfur, but yet there are no alkene epoxidation report (Inorg Chem, 1998,37:6780-6784).
Summary of the invention
The method that the purpose of this invention is to provide a kind of eco-friendly biological enzyme synthesizing epoxy compound by olefin.This method is solvent with water, is oxygen source with hydrogen peroxide or oxygen, and reaction at normal temperatures and pressures, reaction finish after product and separate automatically with solvent, are eco-friendly green epoxy compounds synthesis techniques.
For achieving the above object, the technical solution used in the present invention is:
A kind of method of zyme catalyzing cyclo-olefin oxidation in the aqueous solution, is a biological catalyst with the bromine peroxide enzyme, is oxygen source with hydrogen peroxide or oxygen, and olefin oxidation is become epoxy compounds.
Specific operation process is, in the buffer solution system of PH=4-9, adding is with respect to the bromine peroxide enzyme of buffer solution system bulking value content 0.01-2 (g/L), with respect to the olefin(e) compound of buffer solution system volume content 1-100 (mol/L), with respect to hydrogen peroxide or the aerating oxygen of buffer solution system volume content 0.1-20 (mol/L), under 20～70 ℃ of temperature, stirring reaction 2-10 hour, reaction finishes after product and solvent AUTOMATIC ZONING, obtains the product epoxy compounds.
Described alkene is alkyl alkene or fragrant alkene, as: tetrahydrobenzene, propylene or vinylbenzene etc.; Described damping fluid can provide the damping fluid of similar PH environment for PBS damping fluid, citrate buffer solution, Tris damping fluid or other.
The present invention compared with prior art has following advantage:
1. be catalyzer with reproducible enzyme.The catalyzer that the present invention uses is a bromine peroxide enzyme, this enzyme can extract and dna recombinant expression by biomass regeneration, can realize cheap scale operation, avoided existing chemical catalyst to use scarce resources such as precious metal, have good application prospects from resource view, and avoided the potentially contaminated of heavy metal environment.With the tetrahydrobenzene is example, and hydrogen peroxide is an oxygen source, under 20～75 ℃ of temperature, reacts 2-10 hour, and greater than 50%, the selectivity of epoxy cyclohexane is greater than 85% to the yield of hydrogen peroxide for the product epoxy cyclohexane.
2, eco-friendly green process.Technological operation of the present invention is simple, and enzyme can reuse, and product is easily separated, is oxygen source with hydrogen peroxide and oxygen, and the reaction after product is a water, can not produce other by products of pollution; Solvent is a water, has safe, cheap, eco-friendly characteristics, is unusual ideal Green Chemistry solvent, has avoided the shortcoming of method serious environment pollution such as existing halogenohydrin method, and therefore whole process is eco-friendly Green Chemistry process.
3, reaction system can reuse, and economizes on resources.After synthesizing epoxy compound reaction of the present invention finishes, product separates automatically with reaction system, be reactant, product and water AUTOMATIC ZONING, product is handled easy (water and organic phase AUTOMATIC ZONING, enzyme that is present in aqueous phase etc. can reuse), employed enzyme and aqueous systems can reuse, thereby have reduced discharge of wastewater, have eco-friendly characteristics.
4, reaction conditions gentleness is saved energy consumption.Reaction conditions of the present invention is to carry out under normal temperature, non-pressurized mild conditions, has saved energy consumption greatly.
In a word, the inventive method is to utilize reproducible enzyme catalysis alkene epoxidation, the gentle safety of reaction conditions, cheap, environmental friendliness, conversion rate of reaction product height, selectivity are good, and convenient product separation is quick, do not need special device, enzyme, aqueous systems can reuse, and hydrogen peroxide and oxygen all are the cleaning oxygen source, and is environmentally friendly, entire reaction course is an eco-friendly Green Chemistry process, therefore has wide prospect in industrial application.
Embodiment
Below by specific embodiment method of the present invention and result are described, peroxidase separation and Extraction from marine alga that the present invention uses obtains.
Embodiment 1
The pH=4 that the 10mg bromine peroxide enzyme is joined 50ml is in the PBS damping fluid, adds the 2mol tetrahydrobenzene, when temperature is 25 ℃, adds the hydrogen peroxide reaction beginning of 1mol, stirs 2 hours, leaves standstill and gets organic phase, carries out stratographic analysis.Epoxy cyclohexane is 100% to the hydrogen peroxide yield, epoxy cyclohexane selectivity 90%.
Embodiment 2
The 100mg bromine peroxide enzyme being joined in the citrate buffer solution of pH=7 of 200ml, add the 5mol tetrahydrobenzene again, is 70 ℃ in temperature, with 20ml/min speed aerating oxygen 3mol reaction beginning, stirs 9 hours, leaves standstill and gets organic phase, carries out stratographic analysis.Epoxy cyclohexane to the hydrogen peroxide yield greater than 50%, epoxy cyclohexane selectivity 85%.
Embodiment 3
Reaction among the embodiment 2 is finished the back reuse with isolating enzyme of reaction product and buffering system, adding the 2mol tetrahydrobenzene is 70 ℃ in temperature, adds 0.5mol reaction beginning, stirs 9 hours, leaves standstill and gets organic phase, carries out stratographic analysis.Epoxy cyclohexane is 50% to the hydrogen peroxide yield, epoxy cyclohexane selectivity 90%.
Embodiment 4
The 10mg bromine peroxide enzyme is joined in the PBS damping fluid of pH=4 of 500ml, when temperature is 25 ℃, add the hydrogen peroxide reaction of 8mol, continue to feed third rare 5mol reaction beginning with 10ml/min speed, afterreaction finished in 10 hours.Oxirane ring propane is 10% to the yield of hydrogen peroxide.
Embodiment 5
The 50mg bromine peroxide enzyme is joined in the Tris damping fluid of pH=8 of 100ml, adding 8mol vinylbenzene is 40 ℃ in temperature, adds the hydrogen peroxide reaction beginning of 1mol, and stirring reaction is after 2 hours, leave standstill and get organic phase and carry out stratographic analysis, obtain the Styryl oxide product.
Embodiment 6
The pH=5 that the 50mg bromine peroxide enzyme is joined 1000ml is in the PBS damping fluid, adds the 2mol tetrahydrobenzene, when temperature is 50 ℃, add the hydrogen peroxide reaction beginning of 0.8mol, stirred 3 hours, leave standstill and get organic phase, carry out stratographic analysis, obtain the product epoxy cyclohexane.
Claims (5)
1. method of zyme catalyzing cyclo-olefin oxidation, it is characterized in that: in the aqueous solution, being biological catalyst with the bromine peroxide enzyme, is oxygen source with hydrogen peroxide or oxygen, and olefin oxidation is become epoxy compounds.
2. according to the described method of zyme catalyzing cyclo-olefin oxidation of claim 1, it is characterized in that:
Specific operation process is, in the buffer solution system of PH=4-9, adding is with respect to the bromine peroxide enzyme of buffer solution system bulking value content 0.01-2g/L, with respect to the olefin(e) compound of buffer solution system volume content 1-100mol/L, with respect to hydrogen peroxide or the aerating oxygen of buffer solution system volume content 0.1-20mol/L, under 20～70 ℃ of temperature, stirring reaction 2-10 hour, reaction finishes after product and solvent AUTOMATIC ZONING, obtains the product epoxy compounds.
3. according to claim 1 or 2 described method of zyme catalyzing cyclo-olefin oxidation, it is characterized in that: described alkene is alkyl alkene or fragrant alkene.
4. according to claim 1 or 2 described method of zyme catalyzing cyclo-olefin oxidation, it is characterized in that: described alkene is tetrahydrobenzene, propylene or vinylbenzene.
5. according to the described method of zyme catalyzing cyclo-olefin oxidation of claim 2, it is characterized in that: described damping fluid is PBS damping fluid, citrate buffer solution or Tris damping fluid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006100472559A CN101109016A (en) | 2006-07-21 | 2006-07-21 | Method of zyme catalyzing cyclo-olefin oxidation |
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| CNA2006100472559A CN101109016A (en) | 2006-07-21 | 2006-07-21 | Method of zyme catalyzing cyclo-olefin oxidation |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102071229A (en) * | 2009-11-20 | 2011-05-25 | 中国科学院大连化学物理研究所 | Method for epoxidizing cyclohexene by using enzymatic molecular oxygen |
| CN104837556A (en) * | 2012-10-05 | 2015-08-12 | 康奈尔大学 | Enzymes forming mesoporous assemblies embedded in macroporous scaffolds |
| CN104878052A (en) * | 2015-04-23 | 2015-09-02 | 南京工业大学 | Method for preparing 1, 2-epoxyhexane by adopting fixed bed microchannel reaction device |
| CN105441503A (en) * | 2015-12-21 | 2016-03-30 | 陕西师范大学 | Method for preparing 2,3-epoxy pinane through enzymatic reaction |
| US10792649B2 (en) | 2015-07-15 | 2020-10-06 | Zymtronix, Llc | Automated bionanocatalyst production |
| US10881102B2 (en) | 2015-05-18 | 2021-01-05 | Zymtronix, Llc | Magnetically immobilized microbiocidal enzymes |
| US10993436B2 (en) | 2016-08-13 | 2021-05-04 | Zymtronix Catalytic Systems, Inc. | Magnetically immobilized biocidal enzymes and biocidal chemicals |
-
2006
- 2006-07-21 CN CNA2006100472559A patent/CN101109016A/en active Pending
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102071229A (en) * | 2009-11-20 | 2011-05-25 | 中国科学院大连化学物理研究所 | Method for epoxidizing cyclohexene by using enzymatic molecular oxygen |
| US10767172B2 (en) | 2012-10-05 | 2020-09-08 | Cornell University | Method for epoxidation to produce alkene oxide |
| US11236322B2 (en) | 2012-10-05 | 2022-02-01 | Cornell University | Enzyme forming mesoporous assemblies embedded in macroporous scaffolds |
| US12084649B2 (en) | 2012-10-05 | 2024-09-10 | Cornell University | Hierarchical magnetic nanoparticle-enzyme mesoporous assemblies embedded in macroporous scaffolds |
| US9765324B2 (en) | 2012-10-05 | 2017-09-19 | Cornell University | Hierarchical magnetic nanoparticle enzyme mesoporous assemblies embedded in macroporous scaffolds |
| CN104837556B (en) * | 2012-10-05 | 2018-04-03 | 康奈尔大学 | The mesoporous set that the enzyme being embedded in macropore support is formed |
| CN104837556A (en) * | 2012-10-05 | 2015-08-12 | 康奈尔大学 | Enzymes forming mesoporous assemblies embedded in macroporous scaffolds |
| US10351841B2 (en) | 2012-10-05 | 2019-07-16 | Cornell University | Method for inhibiting growth of microorganisms with macroporous scaffolds |
| CN104878052A (en) * | 2015-04-23 | 2015-09-02 | 南京工业大学 | Method for preparing 1, 2-epoxyhexane by adopting fixed bed microchannel reaction device |
| US11517014B2 (en) | 2015-05-18 | 2022-12-06 | Zymtronix, Inc. | Magnetically immobilized microbiocidal enzymes |
| US10881102B2 (en) | 2015-05-18 | 2021-01-05 | Zymtronix, Llc | Magnetically immobilized microbiocidal enzymes |
| US10792649B2 (en) | 2015-07-15 | 2020-10-06 | Zymtronix, Llc | Automated bionanocatalyst production |
| CN105441503B (en) * | 2015-12-21 | 2019-06-11 | 陕西师范大学 | A kind of method that enzymatic reaction prepares 2,3- epoxypinane |
| CN105441503A (en) * | 2015-12-21 | 2016-03-30 | 陕西师范大学 | Method for preparing 2,3-epoxy pinane through enzymatic reaction |
| US10993436B2 (en) | 2016-08-13 | 2021-05-04 | Zymtronix Catalytic Systems, Inc. | Magnetically immobilized biocidal enzymes and biocidal chemicals |
| US12127557B2 (en) | 2016-08-13 | 2024-10-29 | Zymtronix Catalytic Systems, Inc. | Magnetically immobilized biocidal enzymes and biocidal chemicals |
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