CN102071229A - Method for epoxidizing cyclohexene by using enzymatic molecular oxygen - Google Patents
Method for epoxidizing cyclohexene by using enzymatic molecular oxygen Download PDFInfo
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- CN102071229A CN102071229A CN2009102200425A CN200910220042A CN102071229A CN 102071229 A CN102071229 A CN 102071229A CN 2009102200425 A CN2009102200425 A CN 2009102200425A CN 200910220042 A CN200910220042 A CN 200910220042A CN 102071229 A CN102071229 A CN 102071229A
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Abstract
The invention relates to a method for synthesizing 1,2-epoxy cyclohexane by oxidizing cyclohexene with enzymatic molecular oxygen. The method comprises the following steps of: catalyzing and synthesizing the 1,2-epoxy cyclohexane in buffer solution at the reaction temperature of between 20 and 90 DEG C, wherein the cyclohexene serves as a substrate, bromine peroxidase serves as a catalyst, molecular oxygen serves as an oxygen source and zinc serves as a co-reductant. The method has the characteristics of high reaction selectivity, mild reaction conditions, environmentally friendly processes, no pollution and inexpensive and safe oxygen sources and the like.
Description
Technical field
The present invention relates to a kind of method of enzyme catalysis molecular oxygen oxidation tetrahydrobenzene, specifically a kind of application bromine peroxide enzyme catalytic molecular oxygen cyclohexene oxide generates 1, the method for 2-epoxy cyclohexane.
Background technology
At present, the method for industrial production epoxy cyclohexane mainly contain partition method and chemical synthesis (Speciality Petrochemicals, 1998,5,1-4).Impurities is more in the product that partition method obtains, and often can not satisfy high-quality purity requirement.Chemical synthesis mainly contains chlorohydrination and Halcon method (Halcon method), uses a large amount of hydrochloric acid and caustic soda in the chlorohydrination, causes serious equipment corrosion and environmental pollution easily, also has defectives such as product yield is low, co-product is many, less economical simultaneously.The Halcon method is to react synthesis epoxy cyclohexane by tetrahydrobenzene and superoxide under catalytic condition, process investment is big, technical process is complicated, to raw materials quality have relatively high expectations, joint product are many, and owing to blast easily that to make that operational condition requires very strict.These two kinds of synthetic methods all can not satisfy the requirement of green chemical industry and Sustainable development.
From the applied basic research of tetrahydrobenzene synthesis epoxy cyclohexane, research institution mainly concentrates on the synthetic and the performance study aspect of new catalyst both at home and abroad.Used catalyzer mostly is a transition metal complex, as transition metal molybdenum (VI) (J.Mol.Catal.A:Chem, 2006,248,53-60 etc.), vanadium (V) (J.Mol.Catal.A:Chem, 2002,179,41-51 etc.), manganese (III) (React.Funct.Polym., 2003,56,1-15 etc.) etc. title complex; Transition metal oxide (J.Mol.Catal.A:Chem, 2006,249,123-128 etc.), heteropllyacids (catalysis journal .2002,23,125-126 etc.) and HTS (J Catal., 2002,208,339-344 etc.) etc.But more or less there is following shortcoming in above chemical catalysis: severe reaction conditions, process complexity; Synthetic difficulty of catalyzer or stability are not enough or be difficult to reclaim etc. and cause the catalyzer cost too high; Reaction process is used a large amount of organic solvents, and environmental stress is big; Catalytic efficiency is not high, and selectivity is lower etc.
Along with the pay attention to day by day of people to " Sustainable development ", " recycling economy ", " environmental friendliness manufacturing " and " Green Chemistry ", biocatalysis tetrahydrobenzene synthesis epoxy cyclohexane will become an important directions of cyclohexene ring oxidation research, especially use molecular oxygen to make the catalytic process of oxygen source, because molecular oxygen is cheap and easy to get, environmentally safe is the optimal oxygen source of oxidizing reaction.
Summary of the invention
The object of the invention is to provide a kind of technology simple, eco-friendly catalyzed oxidation tetrahydrobenzene preparation 1, the method for 2-epoxy cyclohexane.
For achieving the above object, the present invention adopts technical scheme to be:
A kind of method of zyme catalyzing cyclo-olefin oxidation in damping fluid, is a catalyzer with the bromine peroxide enzyme, and Potassium Bromide is an auxiliary agent, is oxygen source with the molecular oxygen, is reductive agent with zinc, is 1 with cyclohexene oxide, the 2-epoxy cyclohexane.
Specific operation process is, adding pH in sealed reactor is the damping fluid of 4-9, add Potassium Bromide again with respect to damping fluid volume content 0.02-0.2mmol/ml, bromine peroxide enzyme with respect to damping fluid volume content 5-80u/ml, with respect to buffer system volume content 5-80mg/ml zinc, with respect to buffer system volume content 0.1-0.5ml/ml tetrahydrobenzene, mixing, reactor is sealed, feed molecular oxygen, the gauge pressure of molecular oxygen is 0.05-0.6MPa, reactor is placed 20 ℃ of-90 ℃ of water bath with thermostatic control constant temperature again, the 100-1000rpm magnetic agitation, reacted 0.5-10 hour, and obtained 1,2-epoxy cyclohexane product.
Described bromine peroxide enzyme is the bromine peroxide enzyme that is derived from marine algae coralgal or little coralgal; Described damping fluid can provide one or more the combination in the damping fluid of similar pH environment for citrate buffer solution, Tris damping fluid, phosphate buffered saline buffer or other; Described zinc is the zinc powder of various particle diameters, comprises nano zinc powder.Described molecular oxygen is an air or oxygen, or other oxygen that exist with molecular state.
The present invention compared with prior art has following advantage:
1. use molecular oxygen to make oxygen source, cheap and easy to get, cleanliness without any pollution.
2. reaction preference height, the reaction conditions gentleness, desired reaction temperature and pressure are all lower.
3. use the biological catalyst enzyme to be catalyzer, catalyzer is easy to get.
4. the use bromine peroxide enzyme has good stability (mechanical stability, temperature tolerance, organic solvent tolerance), helps suitability for industrialized production.
Reaction medium simply common, equipment is not had corrosion.The technology green non-pollution, simple, the easy row of operation.
Embodiment
Embodiment 1 (Potassium Bromide 119mg/mol)
In autoclave, add 9.0 milliliters of pH successively and be Tris-hydrochloride buffer, the bromine peroxide enzyme of 400u, 1.0mmol Potassium Bromide, 260 milligrams of zinc powders, 1.0 milliliters of tetrahydrobenzene of 6.0, mixing.Sealed reactor then, and feed 0.40MPa oxygen, and reactor is placed 65 ℃ of waters bath with thermostatic control, 600rpm magnetic agitation.React after 3 hours, reactor taken out, leave standstill cooling after, take out the organic phase liquid in the reaction solution, with gas-matter coupling organic phase is carried out the component structure analysis, the result shows that the catalyzed reaction primary product is 1, the 2-epoxy cyclohexane, micro-2-bromo hexalin and 1 are arranged in addition, 2-two bromo hexanaphthenes, and adopt 1,2-epoxy cyclohexane standard substance addition method is further confirmed, proof principal reaction product really is 1, the 2-epoxy cyclohexane.And with in the organic phase after the gas-chromatography marker method analytical reaction 1,2-epoxy cyclohexane content, as a result 1,2-epoxy cyclohexane accumulation volume is 67.0mg, adopt the peak area normalization method to calculate reaction preference, in the catalytic reaction products 1, the selectivity of 2-epoxy cyclohexane is 93.6%.
Embodiment 2
In autoclave, add 9.0 milliliters of pH successively and be Tris-citrate buffer solution, the bromine peroxide enzyme of 200u, 2.0mmol Potassium Bromide, 130 milligrams of zinc powders, 1.0 milliliters of tetrahydrobenzene of 8.0, mixing.Sealed reactor then, and feed 0.50MPa oxygen, and reactor is placed 65 ℃ of waters bath with thermostatic control, 400rpm magnetic agitation.Magnetic agitation.React after 3 hours, reactor taken out, leave standstill cooling after, take out the organic phase liquid in the reaction solution.Adopt the method identical with embodiment 1 that organic phase is analyzed, analytical results shows that the reaction primary product is 1, the 2-epoxy cyclohexane, and its amount is 53.5mg, in the catalytic reaction products 1,2-epoxy cyclohexane selectivity is 92.9%.
Embodiment 3
In autoclave, add 9.0 milliliters of pH successively and be Tris-citrate buffer solution, the bromine peroxide enzyme of 150u, 1.0mmol Potassium Bromide, 130 milligrams of zinc powders, 1.0 milliliters of tetrahydrobenzene of 6.0, mixing.Sealed reactor then, and feed 0.40MPa oxygen, and reactor is placed 60 ℃ of waters bath with thermostatic control, 600rpm magnetic agitation.Magnetic agitation.React after 3 hours, reactor is taken out, after leaving standstill cooling,, adopt the method identical that organic phase is analyzed with embodiment 1 with 0.5 milliliter of hexanaphthene extractive reaction liquid, analytical results shows, reaction product is mainly 1, the 2-epoxy cyclohexane, and its amount is 27.5mg, in the catalytic reaction products 1,2-epoxy cyclohexane selectivity is 90.9%.
The method has the characteristics such as reaction selectivity height, reaction condition gentleness, technology green non-pollution, the cheap safety of oxygen source.
Claims (6)
1. enzyme catalysis tetrahydrobenzene process for epoxidation, it is characterized in that: in damping fluid, be catalyzer with the bromine peroxide enzyme, Potassium Bromide is an auxiliary agent, is oxygen source with the molecular oxygen, is reductive agent with zinc, is 1 with cyclohexene oxide, the 2-epoxy cyclohexane.
2. it is characterized in that in accordance with the method for claim 1:
Specific operation process is, adding pH in sealed reactor is the damping fluid of 4-9, add Potassium Bromide again with respect to damping fluid volume content 0.02-0.2mmol/ml, bromine peroxide enzyme with respect to damping fluid volume content 5-80u/ml, with respect to buffer system volume content 5-80mg/ml zinc, with respect to buffer system volume content 0.1-0.5ml/ml tetrahydrobenzene, mixing, reactor is sealed, feed molecular oxygen, the gauge pressure of molecular oxygen is 0.05-0.6MPa, reactor is placed 20 ℃ of-90 ℃ of water bath with thermostatic control constant temperature again, the 100-1000rpm magnetic agitation, reacted 0.5-10 hour, and obtained 1,2-epoxy cyclohexane product.
3. according to claim 1 or 2 described methods, it is characterized in that: described bromine peroxide enzyme is the bromine peroxide enzyme that is derived from marine algae coralgal or little coralgal.
4. according to claim 1 or 2 described methods, it is characterized in that: described damping fluid is one or more the combination in citrate buffer solution, Tris damping fluid, the phosphate buffered saline buffer.
5. according to claim 1 or 2 described methods, it is characterized in that: described zinc is zinc powder.
6. according to claim 1 or 2 described methods, it is characterized in that: described molecular oxygen is an air or oxygen.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2009102200425A CN102071229A (en) | 2009-11-20 | 2009-11-20 | Method for epoxidizing cyclohexene by using enzymatic molecular oxygen |
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| CN2009102200425A CN102071229A (en) | 2009-11-20 | 2009-11-20 | Method for epoxidizing cyclohexene by using enzymatic molecular oxygen |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104119380A (en) * | 2014-04-15 | 2014-10-29 | 江苏大明科技有限公司 | Halogen-free oligomerization phosphonate flame retardant and synthesis method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101109016A (en) * | 2006-07-21 | 2008-01-23 | 中国科学院大连化学物理研究所 | Method of zyme catalyzing cyclo-olefin oxidation |
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2009
- 2009-11-20 CN CN2009102200425A patent/CN102071229A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101109016A (en) * | 2006-07-21 | 2008-01-23 | 中国科学院大连化学物理研究所 | Method of zyme catalyzing cyclo-olefin oxidation |
Non-Patent Citations (6)
| Title |
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| PIERRETTE BATTIONI ET AL.: "A New and Efficient Biomimetic System for Hydrocarbon Oxidation by Dioxygen using Manganese Porphyrins, Imidarole, and Zinc", 《J. CHEM. SOC., CHEM. COMMUN.,》 * |
| 于瑶 等: "溴过氧化物酶催化环己烯环氧化反应", 《催化学报》 * |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104119380A (en) * | 2014-04-15 | 2014-10-29 | 江苏大明科技有限公司 | Halogen-free oligomerization phosphonate flame retardant and synthesis method thereof |
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Application publication date: 20110525 |