CN103274883A - Method for preparing lactone through catalyzing oxidation of ketone compound - Google Patents
Method for preparing lactone through catalyzing oxidation of ketone compound Download PDFInfo
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- CN103274883A CN103274883A CN2013102276115A CN201310227611A CN103274883A CN 103274883 A CN103274883 A CN 103274883A CN 2013102276115 A CN2013102276115 A CN 2013102276115A CN 201310227611 A CN201310227611 A CN 201310227611A CN 103274883 A CN103274883 A CN 103274883A
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- carbon nanotube
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Abstract
The invention discloses a method for preparing lactone through catalyzing the oxidation of a ketone compound. The method which treats the ketone compound as a raw material and carbon nanotubes as a catalyst comprises a step of adding an organic solvent and an assistant, and a step of carrying out a catalysis reaction at 25-120DEG C under normal pressure to obtain a lactone compound in a high selectivity manner. The method has the advantages of simple process, mild condition, high selectivity, safety, easy catalyst recovery and the like.
Description
Technical field
The present invention relates to a kind of preparation method of lactone, specifically, relate to the method that a kind of catalyzing ketone compound oxidation prepares lactone.
Background technology
Lactone is a kind of important organic synthesis intermediate, is widely used in polycaprolactone (PCL) and the blending and modifying resin of synthetic various different purposes as 6-caprolactone.Preparing by the Baeyer-Villiger oxidizing reaction in the method for lactone at present, the oxygenant that adopts all is organic peracid such as Peracetic Acid, benzoyl hydroperoxide etc. usually, use not only cost height but also in actually operating, exist many potential safety hazards of such oxygenant, make the practical application of this technology be restricted.
Therefore, by the Baeyer-Villiger oxidizing reaction, adopt environment-friendly, safe oxygen/air to prepare lactone as oxygenant and enjoy people's attention.Patent (CN102408404A) has reported to be the method that the oxidation of oxidizer catalytic pimelinketone prepares caprolactone with oxygen, and this method has been used azo type free base initiator in reaction process, have safety issue, practical application.Panda has reported with oxygen to be oxygenant, and zirconium phosphide is method (the Panda A B. that the oxidation of catalyst ketone compounds prepares lactone
Et al.Catalysis Science ﹠amp; Technology,
2012,
2, 2375-2382), need to use metal catalyst in this method.
Summary of the invention
The object of the invention is to provide a kind of and need not to use metal catalyst, mild condition, safe catalysis of pimelinketone oxidation to prepare the method for 6-caprolactone.
For achieving the above object, the present invention adopts following technical scheme:
Being raw material with the ketone compounds, is oxygenant with oxygen or air, adds organic solvent and auxiliary agent phenyl aldehyde, is catalyzer with the carbon nanotube of many walls or single wall, and under normal pressure, the control temperature of reaction is to carry out catalyzed reaction under 25 ~ 120 ℃ the condition.
Carbon nanotube described in the present invention is to be selected from a kind of in hydroxylation carbon nanotube, carboxylic carbon nano-tube, the carbonylation carbon nanotube, and the mol ratio of auxiliary agent phenyl aldehyde and raw ketone is 1 ~ 4, the preferred 30-60 of temperature of reaction ℃.Organic solvent is 1,2-ethylene dichloride, toluene, phenylfluoroform, ethyl acetate, sec-butyl acetate, 1, a kind of in 4-dichloro six ring.
It is catalyzer that the present invention adopts carbon nanotube, phenyl aldehyde is auxiliary agent, the catalysis of pimelinketone oxidation generates 6-caprolactone under the condition of oxygen or air existence, carbon nanotube can store the free radical that produces in the reaction process, improved the utilising efficiency of auxiliary agent, and for the propagation process of free radical provides assurance, accelerated the complexing of active specy benzoyl hydroperoxide and ketone, be conducive to the generation of 6-caprolactone.
Compared with prior art, the present invention has following beneficial effect:
1. adopting oxygen/air is oxygenant, has avoided the safety issue of using peracid to bring.
2. the present invention uses carbon nanotube as catalyzer, need not to use metal catalyst.
3. technology of the present invention is simple, product separates easily, catalyzer can reuse, and has favorable industrial application prospect.
Embodiment
The present invention will be further described below in conjunction with embodiment, but protection scope of the present invention is not limited to the scope that embodiment represents.
Reagent, catalyzer used among the embodiment are commercially available analytical reagent and sample.
Embodiment 1
Contain in the ethyl acetate solution of 5mg hydroxylation multi-walled carbon nano-tubes at 10mL, add the pimelinketone of 2mmol and the phenyl aldehyde of 2mmol, aerating oxygen, be 25 ℃ of following stirring reactions 4 hours in temperature, analyze after testing, the transformation efficiency of pimelinketone is 85%, and the selectivity of 6-caprolactone is greater than 99%.
Embodiment 2
Contain 1 of the carboxylated multi-walled carbon nano-tubes of 10mg at 10 mL, in the 2-dichloroethane solution, add the 4-methylcyclohexanone of 2mmol and the phenyl aldehyde of 8mmol, be 120 ℃ of following stirring reactions 5 hours in temperature, analyze after testing, the transformation efficiency of 4-methylcyclohexanone is that the selectivity of 97%, 4-methyl cyclohexane lactone is greater than 99%.
Embodiment 3
Contain in the sec-butyl acetate solution of the carboxylated Single Walled Carbon Nanotube of 10mg at 10 mL, adding the 2-Buddha's warrior attendant ketone of 2mmol and the phenyl aldehyde of 6mmol, is 30 ℃ of following stirring reactions 8 hours in temperature, analyzes after testing, the transformation efficiency of 2-Buddha's warrior attendant ketone is that the selectivity of 92%, 2-Buddha's warrior attendant lactone is greater than 99%.
Embodiment 4
Contain in the phenylfluoroform solution of 5mg hydroxylation Single Walled Carbon Nanotube at 10 mL, adding the 3-hexanone of 2mmol and the phenyl aldehyde of 4mmol, is 60 ℃ of following stirring reactions 6 hours in temperature, analyzes after testing, the transformation efficiency of benzophenone is 98%, and the selectivity of propyl propionate is greater than 99%.
Embodiment 5
Contain 1 of 10mg carbonylation multi-walled carbon nano-tubes at 10 mL, in the 4-dichloro six ring solution, add the benzophenone of 2mmol and the phenyl aldehyde of 4mmol, be 80 ℃ of following stirring reactions 6 hours in temperature, analyze after testing, the transformation efficiency of pimelinketone is 90%, and the selectivity of phenol benzoate is greater than 99%.
Embodiment 6
Contain in the ethyl acetate solution of the carboxylated Single Walled Carbon Nanotube of 5mg at 10 mL, adding the methyln-hexyl ketone of 2mmol and the phenyl aldehyde of 2mmol, is 40 ℃ of following stirring reactions 8 hours in temperature, analyzes after testing, the transformation efficiency of pimelinketone is 93%, and the selectivity of hexyl acetate is greater than 99%.
Embodiment 7
Contain in the toluene solution of 10mg hydroxylation multi-walled carbon nano-tubes at 10 mL, adding the cyclopentanone of 2mmol and the phenyl aldehyde of 4mmol, is 60 ℃ of following stirring reactions 8 hours in temperature, analyzes after testing, the transformation efficiency of pimelinketone is 93%, and the selectivity of ring valerolactone is greater than 99%.
Embodiment 8
Contain in the phenylfluoroform solution of the carboxylated Single Walled Carbon Nanotube of 5mg at 10 mL, adding the 2-methylcyclohexanone of 2mmol and the phenyl aldehyde of 2mmol, is 80 ℃ of following stirring reactions 6 hours in temperature, analyzes after testing, the transformation efficiency of pimelinketone is that the selectivity of 80%, 2-methyl cyclohexane lactone is greater than 99%.
Claims (5)
1. a catalyzing ketone compound oxidation prepares the method for lactone, it is characterized in that comprising the steps: with the ketone compounds to be raw material, be oxygenant with oxygen or air, add organic solvent and auxiliary agent phenyl aldehyde, carbon nanotube with many walls or single wall is catalyzer, under normal pressure, the control temperature of reaction is to carry out catalyzed reaction under 25 ~ 120 ℃ the condition.
2. method according to claim 1 is characterized in that described carbon nanotube is selected from a kind of in hydroxylation carbon nanotube, carboxylic carbon nano-tube, the carbonylation carbon nanotube.
3. method according to claim 1 is characterized in that, the mol ratio of auxiliary agent phenyl aldehyde and raw ketone is 1 ~ 4.
4. method according to claim 1 is characterized in that temperature of reaction is 30 ~ 60 ℃.
5. method according to claim 1 is characterized in that described organic solvent is 1,2-ethylene dichloride, toluene, phenylfluoroform, ethyl acetate, sec-butyl acetate, 1, a kind of in 4-dichloro six ring.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106397386A (en) * | 2016-09-13 | 2017-02-15 | 华南理工大学 | Method used for preparing epsilon-hexanolactone |
| CN108558819A (en) * | 2018-04-24 | 2018-09-21 | 华南理工大学 | A method of preparing 6-caprolactone using carbon nanotube |
| WO2019104850A1 (en) * | 2017-11-28 | 2019-06-06 | 浙江大学 | Method for preparing lactone compound |
| CN110922385A (en) * | 2019-12-23 | 2020-03-27 | 华南理工大学 | Method for preparing epsilon-caprolactone by oxidation of non-solvating cyclohexanone-benzaldehyde |
| CN111018823A (en) * | 2019-12-12 | 2020-04-17 | 河南能源化工集团研究总院有限公司 | Process for preparing epsilon-caprolactone and co-producing methacrylic acid by cyclohexanone |
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| CN102603446A (en) * | 2012-02-13 | 2012-07-25 | 湖南大学 | Method for preparing organic lactone by catalyzing and oxidizing organic ketone with carbon materials |
| US20130123514A1 (en) * | 2010-05-28 | 2013-05-16 | Graphea, Inc. | Carbocatalysts for chemical transformations |
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| CN1304933A (en) * | 2000-12-13 | 2001-07-25 | 中国科学院山西煤炭化学研究所 | Process for preparing gamma-butyrolactone |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106397386A (en) * | 2016-09-13 | 2017-02-15 | 华南理工大学 | Method used for preparing epsilon-hexanolactone |
| WO2018049733A1 (en) * | 2016-09-13 | 2018-03-22 | 华南理工大学 | Method for preparing ε-caprolactone |
| CN106397386B (en) * | 2016-09-13 | 2019-05-14 | 华南理工大学 | A method of preparing 6-caprolactone |
| US10710974B2 (en) | 2016-09-13 | 2020-07-14 | South China University Of Technology | Method for preparing epsilon-caprolactone |
| WO2019104850A1 (en) * | 2017-11-28 | 2019-06-06 | 浙江大学 | Method for preparing lactone compound |
| CN108558819A (en) * | 2018-04-24 | 2018-09-21 | 华南理工大学 | A method of preparing 6-caprolactone using carbon nanotube |
| CN111018823A (en) * | 2019-12-12 | 2020-04-17 | 河南能源化工集团研究总院有限公司 | Process for preparing epsilon-caprolactone and co-producing methacrylic acid by cyclohexanone |
| CN110922385A (en) * | 2019-12-23 | 2020-03-27 | 华南理工大学 | Method for preparing epsilon-caprolactone by oxidation of non-solvating cyclohexanone-benzaldehyde |
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| CN103274883B (en) | 2016-04-13 |
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