CN101250565A - Method for preparing 1,2-epoxy cyclohexane by catalytic oxidation of cyclohexene by lipase - Google Patents
Method for preparing 1,2-epoxy cyclohexane by catalytic oxidation of cyclohexene by lipase Download PDFInfo
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- CN101250565A CN101250565A CNA2007101800413A CN200710180041A CN101250565A CN 101250565 A CN101250565 A CN 101250565A CN A2007101800413 A CNA2007101800413 A CN A2007101800413A CN 200710180041 A CN200710180041 A CN 200710180041A CN 101250565 A CN101250565 A CN 101250565A
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- hydrogen peroxide
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- tetrahydrobenzene
- epoxy cyclohexane
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/584—Recycling of catalysts
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Abstract
The invention relates to a method for preparing 1,2-cyclohexene oxide through catalyzing oxidation of cyclohexene with lipase, which comprises following steps: adding cyclohexene into a reaction vessel which is arranged in constant temperature water bath, mixing and stirring dissolvent and organic acid evenly, then, adding catalyst, adding hydrogen peroxide in drops to react, filtering and reclaiming enzyme catalyst, transferring filter liquor into a separating funnel, separating an organic phase, washing to neutrality, then, distilling, and obtaining the product 1,2-cyclohexene oxide. The invention has simple operation process and temperate reaction conditions, the organic acid, the dissolvent and the enzyme catalyst which are added can be reclaimed and used evenly, the other raw material hydrogen peroxide is transformed into water after reaction, which prevents a large amount of industrial pollution from producing, simultaneously, the raw materials can be saved, the product cost is comparatively low, the method accords with the requirements of green chemistry and atom economy at present.
Description
Technical field
The present invention relates to a kind ofly at lipase, catalyzed oxidation tetrahydrobenzene preparation 1 under hydrogen peroxide and the organic acid acting in conjunction, the method for 2-epoxy cyclohexane.
Background technology
1, having many uses of 2-epoxy cyclohexane, be not only and ask in the important organic synthesis that body (can be used for preparing agricultural chemicals propargite, hexanodioic acid, nylon 66, epoxy resin coating, rubber accelerator, dyestuff, medicine etc., also can be used for preparing polymer conditioning agent, tensio-active agent etc.), also be the very strong organic solvent of a kind of dissolving power simultaneously.In addition, because 1, the existence of very active epoxy group(ing) in the 2-epoxy cyclohexane molecular structure makes it generate a series of compounds that have than high added value with substance reaction such as ammonia, amine, phenol, alcohol, carboxylic acid.
Existing epoxy cyclohexane output is lower, a part be by tetrahydrobenzene and hypochlorous acid through addition reaction, use sodium-hydroxide treatment again, dehalogenation closed loop and getting.This method cost is higher, and causes environmental pollution easily; Another part is to reclaim in the light oil waste liquid that produces from caprolactam production to extract to obtain.Not only purity does not reach requirement (generally having only 80%), and because raw material is limited, its output also can not be met the need of market far away; In addition, adopt Peracetic Acid oxidation style preparation in addition, after promptly making catalyzer and make Peracetic Acid with sulfuric acid, further cyclohexene oxide and getting, the reaction process complexity, by product is more, and easily decomposes because of Peracetic Acid, causes 1, and 2-epoxy cyclohexane productive rate is lower.
Summary of the invention
The object of the present invention is to provide a kind of lipase-catalyzed cyclohexene oxide preparation 1, the method of 2-epoxy cyclohexane, this method are to add tetrahydrobenzene at the reaction vessel that places water bath with thermostatic control, after solvent and organic acid mixing stir evenly, add catalyzer again, drip hydrogen peroxide and react, the filtered and recycled enzyme catalyst, filtrate moves in the separating funnel, tell organic phase, be washed to the smart slide in neutral back, obtain product 1, the 2-epoxy cyclohexane.This method operating procedure is simple, the reaction conditions gentleness, all recyclable the recycling of organic acid, solvent and enzyme catalyst that adds, another kind of raw material hydrogen peroxide is converted into free of contamination water after reaction, avoided producing a large amount of industrial pollution, simultaneously conservation, product cost are lower, meet the requirement of current Green Chemistry and Atom economy.
Lipase-catalyzed cyclohexene oxide preparation 1 of the present invention, the method for 2-epoxy cyclohexane follows these steps to carry out:
A, tetrahydrobenzene is added in the reaction vessel, add methylene chloride or ethylene dichloride or trichloromethane or solvent-free and organic acid formic acid or acetate and mix and stir evenly the back and add catalyzer novo435;
B, above-mentioned reaction vessel is placed water bath with thermostatic control, stir down and slowly drips hydrogen peroxide, bath temperature is 30-60 ℃, and the reaction times is 4-16 hour;
After c, reaction finish, filtering recovering catalyst, filtrate places the separating funnel standing demix, tells organic phase;
D, organic phase are washed till rectifying in the neutral and dry organic phase dislocation packing tower of crossing, and collect 125-132 ℃ of cut, are product 1, the 2-epoxy cyclohexane.
Tetrahydrobenzene among the step a: solvent: organic acid: the mass ratio of catalyzer novo435 is 1: 1.5-3.5: 0.8-1.5: 0.025-0.045.
The mass ratio of tetrahydrobenzene and hydrogen peroxide is that the mass ratio of tetrahydrobenzene and hydrogen peroxide is 1 among the step b: 1-2, concentration of hydrogen peroxide are 10%-50%.
Among the step b the preferred 45-50 of the temperature of water bath with thermostatic control ℃, preferred 6-8 of reaction times hour.
Steps d rectifying reflux ratio is 1: 1.
What the present invention relates to is synthetic 1, and the method for 2-epoxy cyclohexane is to be raw material by tetrahydrobenzene and hydrogen peroxide, reacts to obtain product under the condition of making catalyzer in the presence of the organic acid with lipase novo435, and reaction formula is:
At first be that organic acid forms peroxy acid with hydroperoxidation under lipase-catalyzed effect; The peroxy acid that forms generates the product epoxy cyclohexane in organic phase and the reaction of raw material tetrahydrobenzene, and peroxy acid consumes and is converted into acid turns back to that aqueous phase continues and hydroperoxidation formation peroxy acid under lipase-catalyzed effect, has realized the recycle of raw material.The tetrahydrobenzene transformation efficiency is 79.0%, 1, and 2-epoxy cyclohexane selectivity reaches 99.2%.
Synthetic 1, the method operating procedure of 2-epoxy cyclohexane is simple, the reaction conditions gentleness, the organic acid, solvent and the enzyme catalyst that add all can be recycled, another kind of raw material hydrogen peroxide is converted into free of contamination water after reaction, avoided producing a large amount of industrial pollution, simultaneously conservation, product cost are lower, meet the requirement of current Green Chemistry and Atom economy.
Description of drawings
Fig. 1 is reaction mechanism figure of the present invention, R=H wherein, CH
3
Embodiment
Further specify this invention below in conjunction with embodiment
Embodiment 1
In the flask of 150ml, add 8.0g tetrahydrobenzene, 6.5g acetate, 16g methylene chloride, 0.045g catalyzer novo435;
In the temperature that has magnetic agitation is 30 ℃ thermostat water bath, slowly begin to drip 12g concentration and be 30% hydrogen peroxide, dropwised in one hour, under 30 ℃ of these temperature, continue reaction 8 hours then;
Reaction finishes after-filtration and removes enzyme catalyst, and filtrate moves into layering in the separating funnel, gets organic phase and is washed to neutrality, uses anhydrous Na
2SO
4Rectifying in the dislocation packing tower of dry back, reflux ratio is 1: 1, collects 125-132 ℃ of cut, is product 1, the 2-epoxy cyclohexane.
The tetrahydrobenzene per pass conversion is 79.0%, 1, and 2-epoxy cyclohexane selectivity reaches 99.2%, and purity reaches 99.5%
Embodiment 2
In the flask of 150ml, add 8.0g tetrahydrobenzene, 10.5g formic acid, 20g methylene chloride, 0.035g catalyzer novo435;
In the temperature that has magnetic agitation is 45 ℃ thermostat water bath, slowly begin to drip 16g concentration and be 10% hydrogen peroxide, dropwised in one hour, under 45 ℃ of temperature, continue reaction 6 hours then;
Reaction finishes after-filtration and removes enzyme catalyst, and filtrate moves into layering in the separating funnel, gets organic phase and is washed to neutrality, uses anhydrous Na
2SO
4Rectifying in the dislocation packing tower of dry back, reflux ratio is 1: 1, collects 125-132 ℃ of cut, is product 1, the 2-epoxy cyclohexane.
The tetrahydrobenzene per pass conversion is 71.3%, 1, and 2-epoxy cyclohexane selectivity reaches 90.0%, and purity reaches 98.7%
Embodiment 3
In the flask of 150ml, add 8.0g tetrahydrobenzene, 12g acetate, 0.025g catalyzer novo435;
In the temperature that has magnetic agitation is 50 ℃ thermostat water bath, slowly begin to drip 15g concentration and be 20% hydrogen peroxide, dropwised in one hour, under 50 ℃ of temperature, continue reaction 4 hours then;
Reaction finishes after-filtration and removes enzyme catalyst, and filtrate moves into layering in the separating funnel, gets organic phase and is washed to neutrality, uses anhydrous Na
2SO
4Rectifying in the dislocation packing tower of dry back, reflux ratio is 1: 1, collects 125-132 ℃ of cut, is product 1, the 2-epoxy cyclohexane.
The tetrahydrobenzene per pass conversion is 59.4%, 1, and 2-epoxy cyclohexane selectivity reaches 85.1%, purity reaches 92.6%
Embodiment 4
In the flask of 150ml, add 8.0g (10ml) tetrahydrobenzene, 6.4g formic acid, 12g solvent ethylene dichloride, 0.045g catalyzer novo435;
In the temperature that has magnetic agitation is 60 ℃ thermostat water bath, slowly begin to drip 8g concentration and be 50% hydrogen peroxide, dropwised in one hour, under 60 ℃ of these temperature, continue reaction 16 hours then;
Reaction finishes after-filtration and removes enzyme catalyst, and filtrate moves into layering in the separating funnel, gets organic phase and is washed to neutrality, uses anhydrous Na
2SO
4Rectifying in the dislocation packing tower of dry back, reflux ratio is 1: 1, collects 125-132 ℃ of cut, is product 1, the 2-epoxy cyclohexane.
The tetrahydrobenzene per pass conversion is 74.0%, 1, and 2-epoxy cyclohexane selectivity reaches 94.0%, and purity reaches 98.2%
Embodiment 5
In the flask of 150ml, add 8.0g tetrahydrobenzene, 10g acetate, 16g methylene chloride, 0.025g catalyzer novo435;
In the temperature that has magnetic agitation is 47 ℃ thermostat water bath, slowly begin to drip 8g concentration and be 50% hydrogen peroxide, dropwised in one hour, under 47 ℃ of temperature, continue reaction 10 hours then;
Reaction finishes after-filtration and removes enzyme catalyst, and filtrate moves into layering in the separating funnel, gets organic phase and is washed to neutrality, uses anhydrous Na
2SO
4Rectifying in the dislocation packing tower of dry back, reflux ratio is 1: 1, collects 125-132 ℃ of cut, is product 1, the 2-epoxy cyclohexane.
The tetrahydrobenzene per pass conversion is 72.4%, 1, and 2-epoxy cyclohexane selectivity reaches 98.4%, and purity reaches 99.3%
Measure above product physical and chemical performance:
Boiling point: 129 ℃; Refractive index: 1.4521; Proportion: 0.966; Flash-point: 27.2 ℃;
IR：υ
as(C-H)：2936cm
-1，υ
S(C-H)：2860cm
-1，ρ
as(C-H)：1437cm
-1，υ
S(C-O-C)：1259cm
-1，υ
aS(C-O-C)：966cm
-1、780cm
-1。
Claims (6)
1. lipase-catalyzed cyclohexene oxide preparation 1, the method for 2-epoxy cyclohexane is characterized in that following these steps to carrying out:
A, tetrahydrobenzene is added in the reaction vessel, add methylene chloride or ethylene dichloride or trichloromethane or solvent-free and organic acid formic acid or acetate and mix and stir evenly the back and add catalyzer novo435;
B, reaction vessel is placed water bath with thermostatic control, stir down and slowly drips hydrogen peroxide, bath temperature is 30-60 ℃, and the reaction times is 4-16 hour;
After c, reaction finish, filtering recovering catalyst, filtrate places the separating funnel standing demix, tells organic phase;
D, be washed till rectifying in the neutral and dry organic phase dislocation packing tower of crossing, collect 125 1 132 ℃ of cuts, be product 1, the 2-epoxy cyclohexane.
2. preparation method according to claim 1 is characterized in that tetrahydrobenzene among the step a: solvent: organic acid: the mass ratio of catalyzer novo435 is 1: 1.5-3.5: 0.8-1.5: 0.025-0.045.
3. preparation method according to claim 1 is characterized in that the mass ratio of tetrahydrobenzene and hydrogen peroxide is 1 among the step b: 1-2.
4. preparation method according to claim 1 is characterized in that concentration of hydrogen peroxide is 10%-50% among the step b.
5. preparation method according to claim 1 is characterized in that the preferred 45-50 of temperature ℃ of water bath with thermostatic control among the step b, preferred 6-8 of reaction times hour.
6. preparation method according to claim 1 is characterized in that steps d rectifying reflux ratio is 1: 1.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007101800413A CN101250565A (en) | 2007-12-11 | 2007-12-11 | Method for preparing 1,2-epoxy cyclohexane by catalytic oxidation of cyclohexene by lipase |
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|---|---|---|---|
| CNA2007101800413A CN101250565A (en) | 2007-12-11 | 2007-12-11 | Method for preparing 1,2-epoxy cyclohexane by catalytic oxidation of cyclohexene by lipase |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104878052A (en) * | 2015-04-23 | 2015-09-02 | 南京工业大学 | Method for preparing 1,2-epoxyhexane by using fixed-bed micro-channel reaction device |
| CN105693887A (en) * | 2016-03-08 | 2016-06-22 | 华南理工大学 | Preparation method of epoxidised polybutadiene |
| CN112760345A (en) * | 2019-11-01 | 2021-05-07 | 南京盛德生物科技研究院有限公司 | Process for preparing epoxyalkane by enzyme method |
| CN114350737A (en) * | 2022-01-14 | 2022-04-15 | 台州仙琚药业有限公司 | Preparation method of 5 alpha, 6 alpha-epoxy-11 beta, 17 alpha-dihydroxypregn-3, 20-diethylene glycol ketal |
-
2007
- 2007-12-11 CN CNA2007101800413A patent/CN101250565A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104878052A (en) * | 2015-04-23 | 2015-09-02 | 南京工业大学 | Method for preparing 1,2-epoxyhexane by using fixed-bed micro-channel reaction device |
| CN105693887A (en) * | 2016-03-08 | 2016-06-22 | 华南理工大学 | Preparation method of epoxidised polybutadiene |
| CN112760345A (en) * | 2019-11-01 | 2021-05-07 | 南京盛德生物科技研究院有限公司 | Process for preparing epoxyalkane by enzyme method |
| CN114350737A (en) * | 2022-01-14 | 2022-04-15 | 台州仙琚药业有限公司 | Preparation method of 5 alpha, 6 alpha-epoxy-11 beta, 17 alpha-dihydroxypregn-3, 20-diethylene glycol ketal |
| CN114350737B (en) * | 2022-01-14 | 2023-09-15 | 台州仙琚药业有限公司 | Preparation method of 5 alpha, 6 alpha-epoxy-11 beta, 17 alpha-dihydroxypregna-3, 20-diethylene glycol ketal |
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Open date: 20080827 |