Loaded type salen manganese complex catalyst, preparation method and application thereof

A manganese complex, supported technology is applied to the supported salen manganese complex catalyst and the field of preparation and application thereof, which can solve the problems of high cost, low catalytic activity, only 20%, etc., and achieves convenient recovery, high catalytic activity, low cost effect

Inactive Publication Date: 2012-07-18
ZHEJIANG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Salen-type manganese complexes are more efficient catalysts for the epoxidation reaction of hydrogen peroxide and olefins, but there is a disadvantage of more complex losses (that is, the catalyst structure is destroyed) during the reaction process.
In order to make up for this shortcoming, some researchers loaded the salen manganese complex on the surface of MCM-41 or SBA-15 mesoporous materials, and prepared a supported salen manganese complex catalyst (Journal of Molecular Catalysis A: Chemical 221 (2004) 201-208; Journal of Catalysis 238(2006) 134-141), but the synthesis process of these two vectors is more complicated and the cost is higher
[0003] It has been reported in the literature that alumina is a supported epoxidation catalyst (Catalysis Today 115 (2006) 117-123), its active component is cerium oxide, but its catalytic activity is too low (substrate conversion rate is less than 10 %); there are also reports in the literature that the Ag catalyst supported by alumina is used to catalyze epoxidation, and the substrate conversion rate is only 20% under harsh reaction conditions (245 °C)

Method used

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  • Loaded type salen manganese complex catalyst, preparation method and application thereof
  • Loaded type salen manganese complex catalyst, preparation method and application thereof
  • Loaded type salen manganese complex catalyst, preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0042] Embodiment 1, a kind of preparation method of loaded type salen manganese complex catalyst, carries out following steps successively:

[0043] 1), γ-alumina surface treatment:

[0044] A. Add 10g of γ-alumina and 0.2g of sodium to 50mL of toluene, stir and reflux for 1.5 hours;

[0045] B. Cool the mixed solution obtained in step A to 5°C, add 1g of 2-chloroethylphosphonyl chloride in 10mL toluene solution dropwise, drop it in about 15 minutes, continue to stir at 5°C for 2 hours after the drop, filter, and the obtained filter Cake I was washed with clear water and then dried (50°C, dried to constant weight), to obtain filter cake I after drying;

[0046] C, filter cake I and 30g ethylamine are reacted 4 hours under the MPa pressure of 0.1~0.5 in autoclave after drying, reaction temperature 50~55 ℃;

[0047] After the reaction is completed, cool down to room temperature, filter, wash the filter cake II with water and then dry (50°C, dry to constant weight); obtain the...

Embodiment 2

[0055] The epoxidation of embodiment 2, styrene

[0056] Add 10 mL of water, 1 mmol of styrene, 0.08 mmol of pyridine N-oxide and 50 mg of the supported salen manganese complex catalyst prepared in Example 1 (that is, about 0.02 mmol of the Salen manganese complex) into the reaction kettle, and slowly drop Add 1.5 mmol of hydrogen peroxide with a mass concentration of 15%, drop it in about 1 hour, and continue the reaction at 0° C. for 5 hours after the drop.

[0057] The obtained reaction product was separated and processed by column chromatography to obtain 120 mg of styrene oxide with a purity of 99%.

[0058] The yield of styrene oxide was 99%, and the ee value was 72%.

Embodiment 3

[0059] The epoxidation of embodiment 3, cyclohexene

[0060] Add 10mL of water, 1mmol of cyclohexene, 0.08mmol of pyridine N-oxide and 50mg of the loaded salen manganese complex catalyst prepared in Example 1 in the reaction kettle, and slowly add 1.5mmol of a 25% mass concentration at 0°C Hydrogen peroxide, drop in about 1 hour, and continue to react at 0°C for 6 hours after the drop.

[0061] The obtained reaction product was separated and processed by column chromatography to obtain 95 mg of epoxycyclohexane with a purity of 99%.

[0062] The yield of epoxycyclohexane was 96%, and the ee value was 65%.

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Abstract

The invention discloses a loaded type salen manganese complex catalyst. A preparation method of the loaded type salen manganese complex catalyst comprises the following three steps that: 1) gamma-alumina surface treatment: reacting gamma-alumina with sodium, then with 2-chloroethyl phosphonic chloride, and with ethylamine; 2) preparation of salen manganese complex: condensing an aldehyde group in 3,5-ditertiary butyl salicylide with one amino group in (1R, 2R)-cyclohexyl-1,2-diamine, then condensing 3-chlorine-2-tertiary butyl salicylide with the other amino group in (1R, 2R)-cyclohexyl-1,2-diamine, and reacting the obtained ligand with manganese acetate so as to generate salen manganese complex; and 3) loading of salen manganese complex: obtaining a loaded type salen manganese complex catalyst. Under the action of the catalyst, olefin is subjected to oxidizing reaction, by taking hydrogen peroxide as an oxide reagent.

Description

technical field [0001] The invention relates to a supported salen manganese complex catalyst, its preparation method and its application in olefin epoxidation reaction. Background technique [0002] Epoxy compounds are organic compounds that are high-value intermediates in the synthesis of chiral target products. Olefin epoxidation using hydrogen peroxide as oxidizing agent is a green synthetic route to synthesize epoxy compounds. The salen-type manganese complex is a relatively efficient catalyst for the epoxidation reaction of hydrogen peroxide and olefins, but there is a disadvantage of a large loss of the complex (that is, the catalyst structure is destroyed) during the reaction process. In order to make up for this shortcoming, some researchers loaded the salen manganese complex on the surface of MCM-41 or SBA-15 mesoporous materials, and prepared a supported salen manganese complex catalyst (Journal of Molecular Catalysis A: Chemical 221 (2004) 201-208; Journal of Ca...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/26C07D303/04C07D301/12
Inventor 陈新志周少东赵倩
Owner ZHEJIANG UNIV
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