CN104592192A - Method for preparing epsilon-caprolactone - Google Patents
Method for preparing epsilon-caprolactone Download PDFInfo
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- CN104592192A CN104592192A CN201510037608.6A CN201510037608A CN104592192A CN 104592192 A CN104592192 A CN 104592192A CN 201510037608 A CN201510037608 A CN 201510037608A CN 104592192 A CN104592192 A CN 104592192A
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- pimelinketone
- caprolactone
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- organic solvent
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D313/00—Heterocyclic compounds containing rings of more than six members having one oxygen atom as the only ring hetero atom
- C07D313/02—Seven-membered rings
- C07D313/04—Seven-membered rings not condensed with other rings
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Abstract
The invention discloses a method for preparing epsilon-caprolactone. The method comprises the following steps: adding cyclohexanone, a catalyst, an oxidant and an auxiliary oxidant into an organic solvent, wherein the catalyst refers to copper chloride or loaded copper chloride, the oxidant refers to oxygen, and the auxiliary oxidant refers to aldehydes; reacting at the temperature of 10-50 DEG C for 8-14 hours under normal pressure conditions, thereby obtaining the epsilon-caprolactone. The method disclosed by the invention has the advantages that the oxidant is environmentally friendly, the catalyst is low in price and easy to prepare and is easily separated from the product, the amount of the auxiliary oxidant is small and the reaction conditions are mild; and moreover, the method is an environment-friendly method for preparing the epsilon-caprolactone.
Description
Technical field
The invention belongs to chemical field, particularly relate to a kind of 6-caprolactone, specifically a kind of method preparing 6-caprolactone.
Background technology
6-caprolactone (ε-CL) is a kind of important organic synthesis intermediate, enjoys people to pay close attention to particularly as the monomer of synthesising biological degraded type polycaprolactone (PCL).Because PCL has good biocompatibility, nontoxicity, biodegradable and good oozes the property of medicine, occupy an important position in medical science and pharmacy field.But the method Financial cost of traditional synthesis ε-CL is higher, and there is the unfriendly property of environment.Thus, find the study hotspot that efficient green synthesis method becomes research preparation ε-CL, people have studied a lot of catalyst system and carry out Baeyer-Villiger oxidizing reaction for catalysis of pimelinketone and prepare ε-CL in recent years.
So far, following four kinds of methods are mainly contained by Catalytic Oxidation of Cyclohexanone for the method for ε-CL: (1) crosses acid oxidation; (2) biological oxidation process; (3) H
2o
2oxidation style.But these methods still exist some drawbacks, as there is potential safety hazard in peracid use procedure; The reaction conditions that biological enzyme needs comparatively strictly keeps the activity of enzyme; H
2o
2there is water generate and cause ε-CL to be hydrolyzed in oxidizing reaction, reduce productive rate.Therefore, the O of wide material sources, environmental protection is adopted
2/ air prepares as oxygenant the concern that ε-CL enjoys people.Sinhamahapatra etc. are catalyzer with Mesoporous zirconium phosphate, O
2/ phenyl aldehyde is as oxygenant, and under normal temperature, 6-caprolactone productive rate is 78%(Sinhamahapatra A, et al. Catal. Sci. Technol., 2012,2,2375 – 2382), although temperature of reaction is lower, productive rate is relatively low; Zhou Xiantai etc. report use Fe (TPP) Cl as catalyzer, at 60 DEG C, O
2/ phenyl aldehyde is as oxygenant, ε-CL selectivity and the productive rate of preparation are respectively 100%, 96%(Xian-Tai Zhou, et al. J. Porphyrins Phthalocyanines., 2008,12:94-100), but catalyst preparation process is complicated, temperature of reaction is higher, the mole dosage of phenyl aldehyde is 15 times of raw material, and do not meet green chemical industry and produce, cost is higher.Nabae etc. have studied and use various carbon materials catalysis O
2/ oxidation of Benzaldehyde system, peroxyester carries out Bayer-Villiger oxidizing reaction, although met Green Chemistry requirement, but desired reaction temperature is higher, the productive rate of ε-CL is the highest can only reach 65%(Nabae Y, Rokubuichi H, et al. Catal., 2013,3,230 236).Therefore, find the ε-CL that catalytic efficiency is high, cost is low, the catalyzer of environmental protection prepares high yield, highly selective for catalysis of pimelinketone, and it is significant to probe into gentle reaction conditions.
Summary of the invention
For the defect existed in above-mentioned prior art, technical problem to be solved by this invention is to provide a kind of method preparing 6-caprolactone, prepared by the described this method catalyzer difficulty that will solve in prior art existing for the method preparing 6-caprolactone, catalytic efficiency is low, react temperature required height, the technical problem that pro-oxidant phenyl aldehyde consumption is many.
A kind of method preparing 6-caprolactone of the present invention, in a certain amount of organic solvent, add pimelinketone, catalyzer, oxygenant, pro-oxidant, described catalyzer is cupric chloride or loading type cupric chloride, described oxygenant is oxygen, described pro-oxidant is aldehydes, the add-on of described organic solvent by its molecular volume with pimelinketone than calculating, i.e. pimelinketone: organic solvent is 1mol:400 ~ 1200ml, the consumption of described catalyzer calculates by the mass ratio of itself and pimelinketone, i.e. pimelinketone: catalyzer is 1:0.025 ~ 0.1, the flow that described oxygen passes into the molar weight of pimelinketone for benchmark, namely the oxygen flow that every 1mol pimelinketone participates in passing into needed for reaction is 640 ~ 1600ml/min, the consumption of described pro-oxidant is by calculating with the mol ratio of its pimelinketone, i.e. pimelinketone: phenyl aldehyde is 1mol:1 ~ 3mol, in condition of normal pressure, at the temperature of 10 ~ 50 DEG C, 6-caprolactone can be obtained after reaction 8 ~ 14h.
Further, described organic solvent is any one in 1,2-ethylene dichloride or ethyl acetate or acetonitrile.
Further, described pro-oxidant is phenyl aldehyde.
The present invention is under the katalysis of cupric chloride or loading type cupric chloride, take aldehydes as pro-oxidant, catalytic molecular oxygen peroxyester prepares 6-caprolactone, this reaction is because employ cupric chloride or loading type cupric chloride as catalyzer, greatly reduce the consumption of pro-oxidant phenyl aldehyde in the past, reduce reaction times and temperature of reaction, and almost no coupling product generates, be easy to later separation operation.Meanwhile, just can carry out under this reaction normal temperature and pressure conditions, and obtain the 6-caprolactone of highly selective and high yield, and oxygen sources is extensive, clean energy, reduces reaction cost, achieves the Green Chemistry process of this reaction.
The present invention describes first using cupric chloride or loading type cupric chloride as catalyzer, and for Catalytic Oxidation of Cyclohexanone for 6-caprolactone, and catalytic effect is good.Catalyzer is easily prepared, easily separated recycling, greatly reduces catalyzer use cost, has good prospects for commercial application.Employ the oxygen of environmental protection as oxygenant, pro-oxidant consumption is few, avoids the dangerous problem using peracid to bring.
The present invention compares with prior art, and its technical progress is significant.The advantages such as the present invention has oxygenant environmental protection, and catalyzer cheapness is easily prepared, be easy to same product separation, and pro-oxidant consumption is few, gentle reaction conditions are a kind of methods of Green synthesis 6-caprolactone.
Embodiment
Below in conjunction with embodiment, the present invention is described further, but protection scope of the present invention is not limited to the scope that embodiment shows.
The transformation efficiency of embodiment cyclohexanone and the yield of 6-caprolactone detect analysis by GC and draw, GC detection computations method take marker method as benchmark, namely be internal standard substance with chlorobenzene, doing with pimelinketone and 6-caprolactone in corresponding pimelinketone/chlorobenzene to mark in curve and 6-caprolactone/chlorobenzene respectively and mark curve, drawing the transformation efficiency of pimelinketone and the yield of 6-caprolactone by marking curve calculation in GC detection combination correspondence afterwards.
embodiment 1the preparation method of loading type copper chloride catalyst
By a small amount of particulate state CuCl
22H
2o puts into watch-glass, puts into vacuum drying oven, and control temperature is 120 DEG C, takes out, obtain anhydrous cupric chloride after drying 6h.Get CuCl
2(1g, 5.8mmol) is dissolved in anhydrous ethanol (10g), by previously dried activated carbon (3g, 0.25mol), directly adds and obtains in solution, places 12h, then at 150 DEG C, stirs, passes into N
2, dry up to solution, finally vacuum-drying at 80 DEG C (Sun X L, Zhao X Y, Jiang Y,
et al. Synthesis of (-)-3-carene-2,5-dione via allylic oxidation of (+)-3-carene [J]. Journal of the Chinese Chemical Society, 2013,60 (1): 103-107.).
embodiment 2
0.12g loading type copper chloride catalyst, 2.45g pimelinketone, 5.30g phenyl aldehyde, 25mL 1 is added successively in there-necked flask, 2-ethylene dichloride, then oxygen 16ml/min is passed under condition of normal pressure, at 25 DEG C, constant temperature stirs 12h, detect finally by GC and analyze, pimelinketone transformation efficiency 94.6%, 6-caprolactone yield is 94.6%.
Wherein the proportioning of pimelinketone used, phenyl aldehyde and 1,2-ethylene dichloride is calculated by mole volume basis, i.e. pimelinketone: phenyl aldehyde: 1,2-ethylene dichloride is 1mol:2mol:1000mL; The add-on of loading type cupric chloride calculates by the mass ratio of itself and pimelinketone, i.e. loading type cupric chloride: pimelinketone is 0.05:1; Oxygen flow is that 640ml/min calculates by the oxygen flow that every 1mol pimelinketone passes into.
embodiment 3
0.06g copper chloride catalyst, 2.45g pimelinketone, 5.30g phenyl aldehyde, 25mL acetonitrile is added successively in there-necked flask, then oxygen 20ml/min is passed under condition of normal pressure, at 25 DEG C, constant temperature stirs 11h, detect finally by GC and analyze, pimelinketone transformation efficiency 87.2%, 6-caprolactone yield is 87.2%.
Wherein the proportioning of pimelinketone used, phenyl aldehyde and acetonitrile is calculated by mole volume basis, i.e. pimelinketone: phenyl aldehyde: acetonitrile is 1mol:2mol:1000mL; The add-on of cupric chloride calculates by the mass ratio of itself and pimelinketone, i.e. cupric chloride: pimelinketone is 0.025:1; Oxygen flow is that 800ml/min calculates by the oxygen flow that every 1mol pimelinketone passes into.
embodiment 4
0.06g copper chloride catalyst, 2.46g pimelinketone, 5.50g phenyl aldehyde, 25mL ethyl acetate is added successively in there-necked flask, then oxygen 16ml/min is passed under condition of normal pressure, at 25 DEG C, constant temperature stirs 12h, detect finally by GC and analyze, pimelinketone transformation efficiency 80.1%, 6-caprolactone yield is 80.1%.
Wherein the proportioning of pimelinketone used, phenyl aldehyde and ethyl acetate is calculated by mole volume basis, i.e. pimelinketone: phenyl aldehyde: ethyl acetate is 1mol:2.07mol:1000mL; The add-on of cupric chloride calculates by the mass ratio of itself and pimelinketone, i.e. cupric chloride: pimelinketone is 0.025:1; Oxygen flow is that 640ml/min calculates by the oxygen flow that every 1mol pimelinketone passes into.
embodiment 5
0.98g loading type copper chloride catalyst, 19.6g pimelinketone, 53.0g phenyl aldehyde, 200mL1 is added successively in there-necked flask, 2-ethylene dichloride, then oxygen 128ml/min is passed under condition of normal pressure, at 25 DEG C, constant temperature stirs 12h, detect finally by GC and analyze, pimelinketone transformation efficiency 93.6%, 6-caprolactone yield is 93.6%.
Wherein the proportioning of pimelinketone used, phenyl aldehyde and 1,2-ethylene dichloride is calculated by mole volume basis, i.e. pimelinketone: phenyl aldehyde: 1,2-ethylene dichloride is 1mol:2.5mol:1000mL; The add-on of loading type cupric chloride calculates by the mass ratio of itself and pimelinketone, i.e. cupric chloride: pimelinketone is 0.05:1; Oxygen flow is that 640ml/min calculates by the oxygen flow that every 1mol pimelinketone passes into.
Claims (3)
1. prepare the method for 6-caprolactone for one kind, it is characterized in that: in a certain amount of organic solvent, add pimelinketone, catalyzer, oxygenant, pro-oxidant, described catalyzer is cupric chloride or loading type cupric chloride, described oxygenant is oxygen, described pro-oxidant is aldehydes, the add-on of described organic solvent by its molecular volume with pimelinketone than calculating, i.e. pimelinketone: organic solvent is 1mol:400 ~ 1200ml, the consumption of described catalyzer calculates by the mass ratio of itself and pimelinketone, i.e. pimelinketone: catalyzer is 1:0.025 ~ 0.1, the flow that described oxygen passes into the molar weight of pimelinketone for benchmark, namely the oxygen flow that every 1mol pimelinketone participates in passing into needed for reaction is 640 ~ 1600ml/min, the consumption of described pro-oxidant is by calculating with the mol ratio of its pimelinketone, i.e. pimelinketone: phenyl aldehyde is 1mol:1 ~ 3mol, in condition of normal pressure, at the temperature of 10 ~ 50 DEG C, 6-caprolactone can be obtained after reaction 8 ~ 14h.
2. a kind of method preparing 6-caprolactone as claimed in claim 1, is characterized in that: described organic solvent is any one in 1,2-ethylene dichloride or ethyl acetate or acetonitrile.
3. a kind of method preparing 6-caprolactone as claimed in claim 1, is characterized in that: described pro-oxidant is phenyl aldehyde.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105233854A (en) * | 2015-11-02 | 2016-01-13 | 兰州大学 | Catalyst for preparing epsilon-caprolactone and preparation method |
| CN105237507A (en) * | 2015-11-02 | 2016-01-13 | 兰州大学 | Preparation method for epsilon-caprolactone |
| CN111482191A (en) * | 2020-05-13 | 2020-08-04 | 厦门大学 | Nickel-based catalyst, preparation method and application thereof, and method for preparing organic ester by catalytic oxidation of organic ketone |
| WO2021047292A1 (en) * | 2019-09-12 | 2021-03-18 | 浙江大学 | NOVEL METHOD FOR CO-PRODUCTION OF CARBOXYLIC ACID BASED ON OXYGEN OXIDATION AND ε-CAPROLACTONE |
| CN113461652A (en) * | 2021-07-07 | 2021-10-01 | 上海应用技术大学 | Method for preparing epsilon-caprolactone by catalytically oxidizing cyclohexanone in presence of molecular oxygen |
| CN114438522A (en) * | 2022-02-15 | 2022-05-06 | 万华化学集团股份有限公司 | Method for preparing epsilon-caprolactone from cyclohexanone |
| CN115286611A (en) * | 2022-08-22 | 2022-11-04 | 华南理工大学 | Method for simultaneously preparing epsilon-caprolactone and propionic acid |
-
2015
- 2015-01-26 CN CN201510037608.6A patent/CN104592192A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| CARSTEN BOLM, ET AL.: "Use of Molecular Oxygen in the Baeyer-Villiger Oxidation The Influence of Metal Catalysts", 《TETRAHEDRON LETTERS》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105233854A (en) * | 2015-11-02 | 2016-01-13 | 兰州大学 | Catalyst for preparing epsilon-caprolactone and preparation method |
| CN105237507A (en) * | 2015-11-02 | 2016-01-13 | 兰州大学 | Preparation method for epsilon-caprolactone |
| CN105237507B (en) * | 2015-11-02 | 2018-08-03 | 兰州大学 | A kind of preparation method of 6-caprolactone |
| CN105233854B (en) * | 2015-11-02 | 2018-10-30 | 兰州大学 | A kind of catalyst and preparation method being used to prepare 6-caprolactone |
| WO2021047292A1 (en) * | 2019-09-12 | 2021-03-18 | 浙江大学 | NOVEL METHOD FOR CO-PRODUCTION OF CARBOXYLIC ACID BASED ON OXYGEN OXIDATION AND ε-CAPROLACTONE |
| CN111482191A (en) * | 2020-05-13 | 2020-08-04 | 厦门大学 | Nickel-based catalyst, preparation method and application thereof, and method for preparing organic ester by catalytic oxidation of organic ketone |
| CN113461652A (en) * | 2021-07-07 | 2021-10-01 | 上海应用技术大学 | Method for preparing epsilon-caprolactone by catalytically oxidizing cyclohexanone in presence of molecular oxygen |
| CN114438522A (en) * | 2022-02-15 | 2022-05-06 | 万华化学集团股份有限公司 | Method for preparing epsilon-caprolactone from cyclohexanone |
| CN115286611A (en) * | 2022-08-22 | 2022-11-04 | 华南理工大学 | Method for simultaneously preparing epsilon-caprolactone and propionic acid |
| CN115286611B (en) * | 2022-08-22 | 2023-08-22 | 华南理工大学 | Method for simultaneously preparing epsilon-caprolactone and propionic acid |
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