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Method for preparing epsilon-caprolactone by using in-situ peroxide

A technology of peroxide and cyclohexanone peroxide, which is applied in the chemical field, can solve the problems such as the decrease in the use efficiency of hydrogen peroxide, the unsatisfactory yield of ε-caprolactone, and the reduction of the selectivity of ε-caprolactone. , to achieve the effects of cheap catalyst, excellent selectivity, and increased reaction yield

Active Publication Date: 2020-12-11
ZHEJIANG UNIV +2
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the amount of sacrificial alcohol used to generate in situ hydrogen peroxide in this strategy is much more consumed than the ketone substrate of the BV reaction, and the yield of ε-caprolactone is not ideal (maximum yield = 54%)
[0003] In summary, there are still several significant problems in the (in situ) hydrogen peroxide oxidation method: one is that due to its lack of reactivity, a higher concentration of hydrogen peroxide is usually required, and there are safety problems; the other is that it is expensive The hexafluoroisopropanol is used as the only excellent solvent, which seriously affects the application of the method in chemical production; the third is that the yield of ε-caprolactone will obviously decrease with the increase of the conversion rate of the substrate; the fourth is the reaction The presence of water in the system can easily lead to the hydrolysis of ε-caprolactone, thereby reducing the selectivity of ε-caprolactone; fifth, the use efficiency of hydrogen peroxide decreases with the progress of the BV reaction

Method used

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  • Method for preparing epsilon-caprolactone by using in-situ peroxide
  • Method for preparing epsilon-caprolactone by using in-situ peroxide
  • Method for preparing epsilon-caprolactone by using in-situ peroxide

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Experimental program
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Effect test

Embodiment 1

[0044]

[0045] Add N-hydroxyphthalimide (NHPI, 75mg, 0.45mmol), azobisisobutyronitrile (AIBN, 38mg, 0.23mmol), diphenylmethanol (1104mg, 6mmol), cyclohexane Ketone (392mg, 4mmol) and ethyl acetate (AcOEt, 1.5mL) were gas exchanged (pure oxygen) three times, and reacted at 75°C for 8 hours. Lower the temperature of the reaction solution to 30°C, add 1,2-bis(3,5-bis(trifluoromethyl)phenyl)diselenide (Se-Cat1, 70mg, 0.12mmol), trifluoroethanol (TFE, 15mL ), continue to react for 6 hours, and obtain 3a 99% (with biphenyl as internal standard, gas phase yield), 4 99% (with biphenyl as internal standard, gas phase yield). The ε-caprolactone product was separated, and the reaction mother liquor was distilled off under reduced pressure to remove the solvent, then 20 mL of ether was added to dissolve, and then extracted with water (10 mL×3), and the aqueous phase was dried by rotary evaporation to obtain 419 mg (92% )ε-caprolactone product with a purity of 97%.

[0046] 4 (ε-capr...

Embodiment 2

[0048]

[0049] Add N-hydroxyphthalimide (NHPI, 75mg, 0.45mmol), azobisisobutyronitrile (AIBN, 38mg, 0.23mmol), and 4,4'-dimethylbenzylmethanol to the three-necked flask (1272mg, 6 mmol), cyclohexanone (392mg, 4mmol) and ethyl acetate (AcOEt, 1.5mL), gas exchange (pure oxygen) three times, and react at 75°C for 8 hours. Lower the temperature of the reaction solution to 30°C, add 1,2-bis(3,5-bis(trifluoromethyl)phenyl)diselenide (Se-Cat1, 70mg, 0.12mmol), trifluoroethanol (TFE, 15mL ), continue to react for 6 hours to obtain 3b 99% (with biphenyl as internal standard, gas phase yield), 4 99% (with biphenyl as internal standard, gas phase yield).

Embodiment 3

[0051]

[0052] Add N-hydroxyphthalimide (NHPI, 75mg, 0.45mmol), azobisisobutyronitrile (AIBN, 38mg, 0.23mmol), 4,4'-di-n-propyldiphenyl Methanol (1608mg, 6mmol), cyclohexanone (392mg, 4mmol) and ethyl acetate (AcOEt, 1.5mL), gas exchanged (pure oxygen) three times, reacted at 75°C for 8 hours. Lower the temperature of the reaction solution to 30°C, add 1,2-bis(3,5-bis(trifluoromethyl)phenyl)diselenide (Se-Cat1, 70mg, 0.12mmol), trifluoroethanol (TFE, 15mL ), continue to react for 6 hours, obtain 3c 99% (with biphenyl as internal standard, gas phase yield), 4 99% (with biphenyl as internal standard, gas phase yield).

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Abstract

The invention discloses a method for preparing epsilon-caprolactone by using in-situ peroxide. The method efficiently utilizes an in-situ peroxide obtained in a process of oxidizing alcohol by oxygento oxidize cyclohexanone into epsilon-caprolactone, i.e., under the catalysis of a catalyst, an alcohol is oxidized into the corresponding ketone while substances such as peroxy hydroxyl or hydrogen peroxide and the like generated in the process are fully utilized, so that the Baeyer Villiger oxidation reaction from cyclohexanone to epsilon-caprolactone is realized. Compared with a previous epsilon-caprolactone synthesis method, the method of the invention has the advantages that the product yield is remarkably increased, the use efficiency of alcohol is further improved, raw materials and reagents are cheap and easy to obtain, operation is easy, reaction conditions are mild, and the method is clean and environmentally friendly.

Description

technical field [0001] The invention belongs to the field of chemistry, and relates to a new method for producing ε-caprolactone based on oxygen oxidation. Background technique [0002] ε-caprolactone monomer is an important chemical intermediate, and its polymer (PCL) is widely used in many fields including medical polymer resins, environmental protection materials, adhesives and coatings due to its excellent performance. Industrially, ε-caprolactone is mainly produced by Baeyer-Villiger (BV) reaction between cyclohexanone and peroxide containing active oxygen. (In-situ) organic peroxyacids (such as peroxybenzoic acid, peroxyacetic acid, trifluoroperoxyacetic acid, etc.) have excellent reactivity and become the most commonly used oxidant (Chem.Lett., 1991, 20, 641; J.Am .Chem.Soc.,1958,80,4079; J.Mol.Catal.A:Chem.,2004,212,237; Angew.Chem.Int.Ed.,2015,54, 11848), but due to its instability, Harsh operating conditions, higher costs and other shortcomings are gradually repl...

Claims

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Application Information

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IPC IPC(8): C07D313/04
CPCC07D313/04
Inventor 李浩然杜仁峰袁浩然姚加王钰李景波陈斌
Owner ZHEJIANG UNIV
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