CN102408404B - Method for preparing epsilon-caprolactone by oxidizing cyclohexanone through molecular oxygen - Google Patents
Method for preparing epsilon-caprolactone by oxidizing cyclohexanone through molecular oxygen Download PDFInfo
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- CN102408404B CN102408404B CN 201110370189 CN201110370189A CN102408404B CN 102408404 B CN102408404 B CN 102408404B CN 201110370189 CN201110370189 CN 201110370189 CN 201110370189 A CN201110370189 A CN 201110370189A CN 102408404 B CN102408404 B CN 102408404B
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Abstract
The invention discloses a method for preparing epsilon-caprolactone by oxidizing cyclohexanone through molecular oxygen, which comprises the following steps of: introducing excessive oxygen into a three-neck flask in which an organic solvent, the cyclohexanone and a pro-oxidant are accommodated, adding an initiator after 5 minutes, reacting at the temperature of between 30 and 55 DEG C for 7 to 28 hours under heating and stirring, cooling to room temperature after reaction is finished, diluting by using ethyl acetate in an amount which is 3 times the volume of a product, filtering to remove a benzoic acid solid, performing rotary evaporation on filtrate at the temperature of 40 DEG C and when the vacuum degree is controlled to be 0.1Mpa, performing column chromatographic separation on a concentrated mixture to obtain the epsilon-caprolactone product. By the method for preparing the epsilon-caprolactone by oxidizing the cyclohexanone through the molecular oxygen, high yield and selectivity of the epsilon-caprolactone can be achieved; and the used oxidant is the oxygen which is wide in source, low in price and environment-friendly, so the oxidation method is a clean method for synthesizing the epsilon-caprolactone.
Description
Technical field
The present invention relates to a kind of method for preparing 6-caprolactone by the oxidation pimelinketone, relate in particular the method that the molecular oxygen oxidation pimelinketone prepares 6-caprolactone.
Background technology
6-caprolactone is a kind of important organic synthesis intermediate.In the synthetic chemistry field, as polymer monomer, it is very wide that its polymkeric substance (PCL) is used, and it can provide for polymkeric substance the chemical property of many practicalities, such as the snappiness of excellence, shock resistance, water resistance etc.Very important effect is arranged at aspects such as resin modified, coating, tackiness agent, polyurethane artificial leather (PU leather) and biomedical engineerings etc.6-caprolactone can also dissolve many fluoropolymer resins as a kind of strong solvent, the solvency power that the resin of some indissolubles is done well.The synthetic method of existing 6-caprolactone mainly contains:
(1) peroxy acid oxidation style: be that oxygenant oxidation pimelinketone prepares 6-caprolactone with peroxy acid namely.Peroxy acid commonly used has peroxyformic acid, Peracetic Acid, Perpropionic Acid, trifluoro Peracetic Acid, benzoyl hydroperoxide, metachloroperbenzoic acid etc.Concentrated and the subsequent purification process of peroxy acid produces higher, the explosive superoxide of concentration pre-synthesis phase that the major technique deficiency of these class methods being, in addition, also there are certain difficulty in the product separation in later stage and the recycling of carboxylic acid.
(2) hydrogen peroxide method: be about to H
2O
2Directly carry out the method that oxidizing reaction generates 6-caprolactone with pimelinketone.Anna Chrobok
[1]Make liquid-phase catalyst Deng human ionic liquid hydrosulfate solution, the oxidation pimelinketone has obtained the 6-caprolactone of 64% productive rate under 68% hydrogen peroxide; Rafael Augusto Steffen
[2]Make catalyzer in the human aluminum oxide, hydrogen peroxide as oxidant oxidation pimelinketone has obtained the caprolactone of 53% transformation efficiency, and selectivity is 98%; Liu Yuan, Chen Changlin and Xu Nanping
[3]As catalyzer, in 70 ℃ of reactions after 4 hours, the transformation efficiency of pimelinketone is 42 % in 10ml acetonitrile and 30% hydrogen peroxide with the magnesium aluminum-hydrotalcite compounds Sb/HT of load Sb, and the 6-caprolactone selectivity is 94 %.Although avoided the concentrated of peroxy acid in the above-mentioned example, but still have following problem: transformation efficiency is lower, severe reaction conditions, transition state intermediate product peroxy acid is under acid and higher temperature conditions, particularly have under the existence of some metal ions and compound thereof very unstable, and 6-caprolactone easily produces polymerization, hydrolysis in the environment of acidity.
Reference
[1]?Anna?Chrobok，Stefan?Baj，Wojciech?Pudlo.Supported?hydrogensulfate?ionic?liquid?catalysis?in?Baeyer-Villiger?reaction.Applied?catalysis.2009，(366):22-28.
[2]?Rafael?Augusto?Steffen，Sergio?Teixeira，Jorge?Sepulveda1.Alumina-?-catalyzed?Baeyer-Villiger?oxidation?of?cyclohexanone?with?hydrogen?peroxide.Journal?of?Molecular?Catalysis?A.2008，(287):?41-44.
[3] Liu Yuan, Chen Changlin, Xu Nanping. the hydrotalcite catalyzed pimelinketone Baeyer-Villiger oxidation of load antimony prepares 6-caprolactone. catalysis journal .2004,25 (10): 801-804.
Summary of the invention
The objective of the invention is provides a kind of method for preparing 6-caprolactone take molecular oxygen as oxygenant oxidation pimelinketone in order to solve above-mentioned technical problem.
Technical solution of the present invention
A kind of method that is prepared 6-caprolactone by the molecular oxygen oxidation pimelinketone, namely in organic solvent, helping under the oxygenizement of aldehydes, pimelinketone is 6-caprolactone by molecular oxygen oxidation, its reaction process schematic diagram is as shown in Figure 1.
Above-mentioned a kind of method that is prepared 6-caprolactone by the molecular oxygen oxidation pimelinketone, concrete steps are as follows:
Excessive oxygen is passed in the there-necked flask that fills organic solvent, pimelinketone and pro-oxidant, add initiator behind the 5min, at 30-55 ℃ of thermostatically heating stirring reaction 7-28h, reaction is cooled to room temperature after finishing, filtering phenylformic acid solid after the ethyl acetate dilution, filtrate is in 40 ℃, control vacuum tightness is that 0.1Mpa is rotated evaporation, obtain containing the mixing solutions of 6-caprolactone after concentrated, the mixing solutions that contains 6-caprolactone of gained is again through column chromatography for separation, as eluent, collect R with ethyl acetate/normal hexane of 1:5
fThe component of ≈ 0.33 finally obtains the 6-caprolactone product;
Described organic solvent is 1,2-ethylene dichloride, ethyl acetate or acetonitrile;
Described pro-oxidant is phenyl aldehyde;
Wherein the proportioning of used pimelinketone, pro-oxidant and organic solvent is calculated by the mole volume ratio, i.e. pimelinketone: pro-oxidant: organic solvent is 1mol:2.2 ~ 2.4mol:280 ~ 635ml;
Described initiator is the mixture that Diisopropyl azodicarboxylate, benzoyl peroxide or Diisopropyl azodicarboxylate and benzoyl peroxide form, and its add-on is pressed the weight ratio of initiator and pimelinketone and calculated, i.e. initiator: pimelinketone is 1:10 ~ 100.
Beneficial effect of the present invention
A kind of method that is prepared 6-caprolactone by the molecular oxygen oxidation pimelinketone of the present invention, i.e. helping under the oxygenizement at aldehydes, pimelinketone is 6-caprolactone by molecular oxygen oxidation, this reaction has realized the selective oxidation under the mild conditions, its selectivity is very high, almost no coupling product is easy to the later separation operation.Simultaneously, molecular oxygen is a kind of clean energy, has realized the Green Chemistry process of reaction.
In addition, a kind of method that is prepared 6-caprolactone by the molecular oxygen oxidation pimelinketone of the present invention, because the adding of initiator can significantly improve the productive rate of 6-caprolactone, maximum output can reach 85.1%, selectivity is 100%.
Description of drawings
Fig. 1, The molecular oxygen oxidation pimelinketone prepares the reaction process schematic diagram of 6-caprolactone.
Embodiment
Also by reference to the accompanying drawings the present invention is further set forth below by embodiment, but do not limit the present invention.
The used main laboratory apparatus of the present invention or equipment:
Various raw materials and reagent that the present invention is used:
The productive rate of 6-caprolactone is calculated as follows:
The productive rate of 6-caprolactone=
=
Embodiment 1
A kind of method that is prepared 6-caprolactone by the molecular oxygen oxidation pimelinketone, concrete steps are as follows:
In there-necked flask, add successively 2g pimelinketone, 5g phenyl aldehyde, 12ml 1, the 2-ethylene dichloride, wherein used pimelinketone, phenyl aldehyde and organic solvent are 1, the proportioning of 2-ethylene dichloride is calculated by the mole volume ratio, be pimelinketone: phenyl aldehyde: 1,2-ethylene dichloride is 1mol:2.35mol:600ml;
After passing into excessive oxygen 5min, add initiator Diisopropyl azodicarboxylate 0.2g, the add-on of initiator is by its weight ratio calculating with pimelinketone, i.e. initiator: pimelinketone is 1:10;
At 40 ℃ of lower constant temperature stirring reaction 8h, reaction is cooled to room temperature after finishing, filtering phenylformic acid solid after the ethyl acetate dilution of 3 times of volumes, filtrate is in 40 ℃, control vacuum tightness is that 0.1Mpa is rotated evaporation, obtains containing pimelinketone, 6-caprolactone, phenyl aldehyde and a small amount of benzoic mixing solutions;
Above-mentioned mixing solutions is by column chromatography for separation, as eluent, collects R with ethyl acetate/normal hexane of 1:5
fThe component of ≈ 0.33 finally obtains 1.98g 6-caprolactone product, and the productive rate of 6-caprolactone finally is 85.1%, and selectivity is 100%.
Embodiment 2
A kind of method that is prepared 6-caprolactone by the molecular oxygen oxidation pimelinketone, concrete steps are as follows:
In there-necked flask, add successively 5g pimelinketone, 12.5g phenyl aldehyde, 14ml 1, the 2-ethylene dichloride, wherein used pimelinketone, phenyl aldehyde and organic solvent are 1, the proportioning of 2-ethylene dichloride is calculated by the mole volume ratio, be pimelinketone: phenyl aldehyde: 1,2-ethylene dichloride is 1mol:2.2mol:280ml;
After passing into excessive oxygen 5min, add initiator Diisopropyl azodicarboxylate 0.5g, the add-on of initiator is by its weight ratio calculating with pimelinketone, i.e. initiator: pimelinketone is 1:10;
45 ℃ of constant temperature stirring reaction 14h, reaction is cooled to room temperature after finishing, filtering phenylformic acid solid after the ethyl acetate dilution of 3 times of volumes, filtrate is in 40 ℃, control vacuum tightness is that 0.1Mpa is rotated evaporation, obtains containing pimelinketone, 6-caprolactone, phenyl aldehyde and a small amount of benzoic mixing solutions;
Above-mentioned mixing solutions is by column chromatography for separation, as eluent, collects R with ethyl acetate/normal hexane of 1:5
fThe component of ≈ 0.33 obtains 4.71 g 6-caprolactone products, and the productive rate of 6-caprolactone is 81.0%, and selectivity is 100%.
Embodiment 3
A kind of method that is prepared 6-caprolactone by the molecular oxygen oxidation pimelinketone, concrete steps are as follows:
In there-necked flask, add 2g pimelinketone, 5g phenyl aldehyde, 12ml1, the 2-ethylene dichloride, wherein used pimelinketone, phenyl aldehyde and organic solvent namely the proportioning of 1,2-ethylene dichloride calculate by the mole volume ratio, be pimelinketone: phenyl aldehyde: 1,2-ethylene dichloride is 1mol:2.35mol:600ml;
After passing into excessive oxygen 5min, add initiator Diisopropyl azodicarboxylate 0.1g, the add-on of initiator is by its weight ratio calculating with pimelinketone, i.e. initiator: pimelinketone is 1:20;
At 30 ℃ of lower constant temperature stirring reaction 8h, reaction is cooled to room temperature after finishing, filtering phenylformic acid solid after the ethyl acetate dilution of 3 times of volumes, filtrate is in 40 ℃, control vacuum tightness is that 0.1Mpa is rotated evaporation, obtains containing pimelinketone, 6-caprolactone, phenyl aldehyde and a small amount of benzoic mixing solutions;
Above-mentioned mixing solutions is by column chromatography for separation, as eluent, collects R with ethyl acetate/normal hexane of 1:5
fThe component of ≈ 0.33 obtains 1.44 g 6-caprolactone products, and the productive rate of 6-caprolactone is 61.9%, and selectivity is 100%.
Embodiment 4
A kind of method that is prepared 6-caprolactone by the molecular oxygen oxidation pimelinketone, concrete steps are as follows:
Add successively 2g pimelinketone, 5g phenyl aldehyde, 11ml ethyl acetate in there-necked flask, pimelinketone, phenyl aldehyde and organic solvent are that the proportioning of ethyl acetate is calculated by the mole volume ratio, i.e. pimelinketone: phenyl aldehyde: ethyl acetate is 1mol:2.35mol:550ml;
After passing into excessive oxygen 5min, add initiator Diisopropyl azodicarboxylate 0.13g, the add-on of initiator is by its weight ratio calculating with pimelinketone, i.e. initiator: pimelinketone is 1:15;
At 40 ℃ of constant temperature stirring reaction 10h, reaction is cooled to room temperature after finishing, filtering phenylformic acid solid after the ethyl acetate dilution of 3 times of volumes, filtrate is in 40 ℃, control vacuum tightness is that 0.1Mpa is rotated evaporation, obtains containing pimelinketone, 6-caprolactone, phenyl aldehyde and a small amount of benzoic mixing solutions;
Above-mentioned mixing solutions is by column chromatography for separation, as eluent, collects R with ethyl acetate/normal hexane of 1:5
fThe component of ≈ 0.33 obtains 1.4g 6-caprolactone product, and the productive rate of 6-caprolactone is 60.2%, and selectivity is 100%.
Embodiment 5
A kind of method that is prepared 6-caprolactone by the molecular oxygen oxidation pimelinketone, concrete steps are as follows:
Add successively 2g pimelinketone, 5g phenyl aldehyde, 13ml acetonitrile in there-necked flask, pimelinketone, phenyl aldehyde and organic solvent are that the proportioning of acetonitrile is calculated by the mole volume ratio, i.e. pimelinketone: phenyl aldehyde: acetonitrile is 1mol:2.35mol:635ml;
After passing into excessive oxygen 5min, add initiator Diisopropyl azodicarboxylate 0.13g, the add-on of initiator is by its weight ratio calculating with pimelinketone, i.e. initiator: pimelinketone is 1:15;
At 40 ℃ of constant temperature stirring reaction 12h, reaction is cooled to room temperature after finishing, filtering phenylformic acid solid after the ethyl acetate dilution of 3 times of volumes, filtrate is in 40 ℃, control vacuum tightness is that 0.1Mpa is rotated evaporation, obtains containing pimelinketone, 6-caprolactone, phenyl aldehyde and a small amount of benzoic mixing solutions;
Above-mentioned mixing solutions is by column chromatography for separation, as eluent, collects R with ethyl acetate/normal hexane of 1:5
fThe component of ≈ 0.33 obtains 0.8 g 6-caprolactone product, and the productive rate of 6-caprolactone is 34.4%, and selectivity is 100%.
Embodiment 6
A kind of method that is prepared 6-caprolactone by the molecular oxygen oxidation pimelinketone, concrete steps are as follows:
In there-necked flask, add successively 2g pimelinketone, 5g phenyl aldehyde, 8ml 1,2-ethylene dichloride, pimelinketone, phenyl aldehyde and the organic solvent i.e. proportioning of 1,2-ethylene dichloride calculate by the mole volume ratio, be pimelinketone: phenyl aldehyde: 1,2-ethylene dichloride is 1mol:2.35mol:400ml;
After passing into excessive oxygen 5min, add initiator benzoyl peroxide 0.2g, the add-on of initiator is by its weight ratio calculating with pimelinketone, i.e. initiator: pimelinketone is 1:10;
At 40 ℃ of constant temperature stirring reaction 7h, reaction is cooled to room temperature after finishing, filtering phenylformic acid solid after the ethyl acetate dilution of 3 times of volumes, filtrate is in 40 ℃, control vacuum tightness is that 0.1Mpa is rotated evaporation, obtains containing pimelinketone, 6-caprolactone, phenyl aldehyde and a small amount of benzoic mixing solutions;
Above-mentioned mixing solutions is by column chromatography for separation, as eluent, collects R with ethyl acetate/normal hexane of 1:5
fThe component of ≈ 0.33 obtains 0.92g 6-caprolactone product, and the productive rate of 6-caprolactone is 39.5%, and selectivity is 100%.
Embodiment 7
A kind of method that is prepared 6-caprolactone by the molecular oxygen oxidation pimelinketone, concrete steps are as follows:
In there-necked flask, add successively 2g pimelinketone, 5g phenyl aldehyde, 8ml 1,2-ethylene dichloride, pimelinketone, phenyl aldehyde and the organic solvent i.e. proportioning of 1,2-ethylene dichloride calculate by the mole volume ratio, be pimelinketone: phenyl aldehyde: 1,2-ethylene dichloride is 1mol:2.35mol:400ml;
After passing into excessive oxygen 5min, add initiator benzoyl peroxide 0.02g and Diisopropyl azodicarboxylate 0.2g, the add-on of initiator benzoyl peroxide and Diisopropyl azodicarboxylate is pressed the weight ratio of benzoyl peroxide, Diisopropyl azodicarboxylate and pimelinketone and calculated, i.e. benzoyl peroxide: Diisopropyl azodicarboxylate: pimelinketone is 1:10:100;
At 40 ℃ of constant temperature stirring reaction 9h, reaction is cooled to room temperature after finishing, filtering phenylformic acid solid after the ethyl acetate dilution of 3 times of volumes, filtrate is in 40 ℃, control vacuum tightness is that 0.1Mpa is rotated evaporation, obtains containing pimelinketone, 6-caprolactone, phenyl aldehyde and a small amount of benzoic mixing solutions;
Above-mentioned mixing solutions is by column chromatography for separation, as eluent, collects R with ethyl acetate/normal hexane of 1:5
fThe component of ≈ 0.33 obtains 1.9g 6-caprolactone product, and the productive rate of 6-caprolactone is 81.7%, and selectivity is 100%.
Control Example 1
A kind of method that is prepared 6-caprolactone by the molecular oxygen oxidation pimelinketone, namely preparation process does not add initiator, and concrete steps are as follows:
In there-necked flask, add successively 2g pimelinketone, 6.5g phenyl aldehyde, 8ml1,2-ethylene dichloride, pimelinketone, phenyl aldehyde and the organic solvent i.e. proportioning of 1,2-ethylene dichloride calculate by the mole volume ratio, be pimelinketone: phenyl aldehyde: 1,2-ethylene dichloride is 1mol:3.1mol:400ml;
After passing into excessive oxygen, at 40 ℃ of constant temperature stirring reaction 8h, reaction is cooled to room temperature after finishing, filtering phenylformic acid solid after the ethyl acetate dilution of 3 times of volumes, filtrate is in 40 ℃, control vacuum tightness is that 0.1Mpa is rotated evaporation, obtains containing pimelinketone, 6-caprolactone, phenyl aldehyde and a small amount of benzoic mixing solutions;
Above-mentioned mixing solutions is by column chromatography for separation, as eluent, collects R with ethyl acetate/normal hexane of 1:5
fThe component of ≈ 0.33 obtains 0.25g 6-caprolactone product, and the productive rate of 6-caprolactone is 10.7%, and selectivity is 100%.
The productive rate results of comparison of the 6-caprolactone by the above embodiments 1～7 gained and the 6-caprolactone of control Example 1 gained shows, adds the productive rate that initiator can significantly improve 6-caprolactone.
Above said content only is the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (7)
1. method that is prepared 6-caprolactone by the molecular oxygen oxidation pimelinketone is characterized in that concrete steps are as follows:
Excessive oxygen is passed in the there-necked flask that fills organic solvent, pimelinketone and pro-oxidant, adds initiator behind the 5min,
At 30-55 ℃ of heated and stirred reaction 7-28h, reaction is cooled to room temperature after finishing, filtering phenylformic acid solid after the ethyl acetate dilution, filtrate is in 40 ℃, control vacuum tightness is that 0.1MPa is rotated evaporation, and the mixing solutions after concentrating is again through column chromatography for separation, as dewatering agent, collect R with ethyl acetate/normal hexane of 1:5
fThe component of ≈ 0.33 finally obtains the 6-caprolactone product;
Described organic solvent is 1,2-ethylene dichloride, acetonitrile or ethyl acetate;
Described pro-oxidant is phenyl aldehyde;
Wherein the proportioning of used pimelinketone, pro-oxidant and organic solvent is calculated by the mole volume ratio, i.e. pimelinketone: pro-oxidant: organic solvent is 1mol:2.2 ~ 2.35mol:280 ~ 635ml;
Described initiator is the mixture that Diisopropyl azodicarboxylate, benzoyl peroxide or Diisopropyl azodicarboxylate and benzoyl peroxide form, and its add-on is pressed the weight ratio of initiator and pimelinketone and calculated, i.e. initiator: pimelinketone is 1:10 ~ 100.
2. a kind of method that is prepared 6-caprolactone by the molecular oxygen oxidation pimelinketone as claimed in claim 1 is characterized in that described organic solvent is 1,2-ethylene dichloride, and described initiator is Diisopropyl azodicarboxylate;
The proportioning of pimelinketone, phenyl aldehyde and 1,2-ethylene dichloride is calculated by the mole volume ratio, i.e. pimelinketone: phenyl aldehyde: 1,2-ethylene dichloride is 1mol:2.35mol:600ml;
The add-on of initiator Diisopropyl azodicarboxylate is initiator by the weight ratio of itself and pimelinketone: pimelinketone is 1:10.
3. a kind of method that is prepared 6-caprolactone by the molecular oxygen oxidation pimelinketone as claimed in claim 1 is characterized in that described organic solvent is 1,2-ethylene dichloride, and described initiator is Diisopropyl azodicarboxylate;
The proportioning of pimelinketone, phenyl aldehyde and 1,2-ethylene dichloride is calculated by the mole volume ratio, i.e. pimelinketone: phenyl aldehyde: 1,2-ethylene dichloride is 1mol:2.2mol:280ml;
The add-on of initiator Diisopropyl azodicarboxylate is initiator by the weight ratio of itself and pimelinketone: pimelinketone is 1:10.
4. a kind of method that is prepared 6-caprolactone by the molecular oxygen oxidation pimelinketone as claimed in claim 1 is characterized in that described organic solvent is 1,2-ethylene dichloride, and described initiator is Diisopropyl azodicarboxylate;
The proportioning of pimelinketone, phenyl aldehyde and 1,2-ethylene dichloride is calculated by the mole volume ratio, i.e. pimelinketone: phenyl aldehyde: 1,2-ethylene dichloride is 1mol:2.35mol:600ml;
The add-on of initiator Diisopropyl azodicarboxylate is initiator by the weight ratio of itself and pimelinketone: pimelinketone is 1:20.
5. a kind of method that is prepared 6-caprolactone by the molecular oxygen oxidation pimelinketone as claimed in claim 1 is characterized in that described organic solvent is ethyl acetate, and described initiator is Diisopropyl azodicarboxylate;
The proportioning of pimelinketone, phenyl aldehyde and ethyl acetate is calculated by the mole volume ratio, i.e. pimelinketone: phenyl aldehyde: ethyl acetate is
1mol:2.35mol：550ml；
The add-on of initiator Diisopropyl azodicarboxylate is initiator by the weight ratio of itself and pimelinketone: pimelinketone is 1:15.
6. a kind of method that is prepared 6-caprolactone by the molecular oxygen oxidation pimelinketone as claimed in claim 1 is characterized in that described organic solvent is acetonitrile, and described initiator is Diisopropyl azodicarboxylate
The proportioning of pimelinketone, phenyl aldehyde and acetonitrile is calculated by the mole volume ratio, i.e. pimelinketone: phenyl aldehyde: acetonitrile is 1mol:2.35mol:635ml;
The add-on of initiator Diisopropyl azodicarboxylate is initiator by the weight ratio of itself and pimelinketone: pimelinketone is 1:15.
7. a kind of method that is prepared 6-caprolactone by the molecular oxygen oxidation pimelinketone as claimed in claim 1 is characterized in that described organic solvent is 1,2-ethylene dichloride, and described initiator is benzoyl peroxide;
The proportioning of pimelinketone, phenyl aldehyde and 1,2-ethylene dichloride is calculated by the mole volume ratio, i.e. pimelinketone: phenyl aldehyde: 1,2-ethylene dichloride is 1 mol:2.35 mol:400 ml;
The add-on of initiator benzoyl peroxide is initiator by the weight ratio of itself and pimelinketone: pimelinketone is 1:10.
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| CN106701859A (en) * | 2017-02-20 | 2017-05-24 | 青岛科技大学 | Process for double-enzyme coupling-chemical synthesis of epsilon-caprolactone |
| CN109836406B (en) * | 2017-11-28 | 2020-06-09 | 浙江大学 | Method for preparing lactone compounds |
| CN112479860B (en) * | 2019-09-12 | 2022-10-04 | 浙江大学 | Novel method for co-production of carboxylic acid and epsilon-caprolactone based on oxygen oxidation |
| CN113461652B (en) * | 2021-07-07 | 2022-10-14 | 上海应用技术大学 | Method for preparing epsilon-caprolactone by catalytically oxidizing cyclohexanone in presence of molecular oxygen |
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| CN101307045A (en) * | 2008-07-11 | 2008-11-19 | 湖南大学 | Method for preparing caprolactone from cyclohexanone by catalytic oxidation |
| CN101412704A (en) * | 2008-10-27 | 2009-04-22 | 南京工业大学 | Preparation of epsilon-caprolactone |
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| CN101307045A (en) * | 2008-07-11 | 2008-11-19 | 湖南大学 | Method for preparing caprolactone from cyclohexanone by catalytic oxidation |
| CN101412704A (en) * | 2008-10-27 | 2009-04-22 | 南京工业大学 | Preparation of epsilon-caprolactone |
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