Baeyer-Villiger oxidation reaction catalyst and preparation method and application thereof

A technology of oxidation reaction and catalyst, applied in the direction of physical/chemical process catalyst, catalytic reaction, organic compound/hydride/coordination complex catalyst, etc. Explosion and other problems, to achieve the effect of novel catalyst structure, constant catalytic activity and easy recycling

Inactive Publication Date: 2016-04-20
SHIJIAZHUANG UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The Baeyer-Villiger reaction with peroxyacid (salt) as oxidizing agent has the following disadvantages: (1) peroxyacid (salt) will produce equivalent acid or salt by-products when carrying out Baeyer-Villiger oxidation reaction to produce ester The product causes waste and does not conform to the principle of atomic economy; (2) peroxyacid is expensive and sensitive to vibration, prone to explosion and dangerous

Method used

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  • Baeyer-Villiger oxidation reaction catalyst and preparation method and application thereof
  • Baeyer-Villiger oxidation reaction catalyst and preparation method and application thereof
  • Baeyer-Villiger oxidation reaction catalyst and preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0021] In a 250mL four-neck flask, add 50mL of water, 2.33g (0.012mol) of CsHCO 3 and 50mL of methanol, stirred, added 3.09g (0.01mol) N-Boc-aspartic acid-4-(4-nitro)benzyl ester, reacted at room temperature for 10min, and added 0.65g (0.003mol) CsHCO 3 , control the pH of the system to 8-9, after the reaction is completed, the methanol is distilled off and dried to obtain 4.40 g of white cesium salt of N-Boc-aspartic acid-4-(4-nitro)benzyl ester.

[0022] In 20 mL of a mixed solvent of DMF and N-methylpyrrolidone (V / V=13:7), add 0.62 g (1.4 mmol) of cesium salt of N-Boc-aspartic acid-4-(4-nitro)benzyl ester , 1.0g Merrifield resin (chlorine content: 0.7mmol / g), N 2 Under protection, stir the reaction at 50°C for 36h, filter, and wash the resin with 5mL×3H 2 O, washed with 5 mL×3 DMF, 5 mL×3 dichloromethane, and dried under vacuum to obtain 1.18 g of the product.

[0023] Add 1.0 g of the resin prepared above into 10 mL of glacial acetic acid (mass fraction: 90%), cool to 0...

Embodiment 2

[0026] Substitute (S)-N-tert-butoxycarbonyl-aspartic acid-4-(4-nitro)benzyl ester for N-tert-butoxycarbonyl-aspartic acid-4-(4-nitro)benzyl ester , and other operations were the same as in Example 1 to obtain (S)-N-tert-butoxycarbonyl-aspartic acid catalyst supported by Merrifield resin, with a loading capacity of 0.66 mmol / g.

Embodiment 3

[0028] Substitute (R)-N-tert-butoxycarbonyl-aspartic acid-4-(4-nitro)benzyl ester for N-tert-butoxycarbonyl-aspartic acid-4-(4-nitro)benzyl ester , and other operations were the same as in Example 1 to obtain (R)-N-tert-butoxycarbonyl-aspartic acid catalyst supported by Merrifield resin, with a loading capacity of 0.67 mmol / g.

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Abstract

The invention discloses a Baeyer-Villiger oxidation reaction catalyst and a preparation method and application thereof. The Baeyer-Villiger oxidation reaction catalyst is N-t-butyloxycarboryl-aspartic acid immobilized by Merrifield resin, (S)-N-t-butyloxycarboryl-aspartic acid immobilized by Merrifield resin and (R)-N-t-butyloxycarboryl-aspartic acid immobilized by Merrifield resin. The preparation method of the catalyst comprises the following steps: 1, forming salt with N-Boc-aspartic acid-4-(4-nitro) benzyl ester and alkali; 2, making N-Boc-aspartic acid-4-(4-nitro) benzyl ester salt and chloromethyl groups on the Merrifield resin be subjected to a substitution reaction, so that N-Boc-aspartic acid-4-(4-nitro) benzyl ester immobilized by the Merrifield resin is obtained; 3, conducting debenzylation on the N-Boc-aspartic acid-4-(4-nitro) benzyl ester immobilized by the Merrifield resin in a Zn-HOAc system with the mass fraction being 90% at the temperature of 0 DEG C, so that the Baeyer-Villiger oxidation reaction catalyst is obtained. Peroxy acid can be generated by the catalyst and H2O2 under a certain condition in an in-situ mode, a Baeyer-Villiger oxidation reaction can be achieved safely and effectively, the product yield is high, a generated carboxylic acid by-product is the catalyst itself, catalyst consumption is little, and the catalyst can be utilized in a repeated and cyclic mode.

Description

technical field [0001] The invention relates to the field of catalytic organic synthesis, in particular to a Baeyer-Villiger oxidation reaction catalyst and its preparation method and application. Background technique [0002] Baeyer-Villiger oxidation is one of the important reactions for the direct synthesis of esters and lactones from ketones. Peroxyacids such as peracetic acid, m-chloroperoxybenzoic acid, potassium persulfate, etc. are commonly used oxidants in Baeyer-Villiger oxidation reactions. The Baeyer-Villiger reaction with peroxyacid (salt) as oxidizing agent has the following disadvantages: (1) peroxyacid (salt) will produce equivalent acid or salt by-products when carrying out Baeyer-Villiger oxidation reaction to produce ester The product causes waste and does not conform to the principle of atomic economy; (2) peroxyacid is expensive, sensitive to vibration, prone to explosion, and dangerous. In contrast, H 2 o 2 As a Baeyer-Villiger reaction oxidant, it ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/08C07D309/30C07D307/33C07D313/04C07D487/08
CPCB01J31/08B01J2231/70C07D307/33C07D309/30C07D313/04C07D487/08
Inventor 史兰香张宝华刘斯婕郭瑞霞
Owner SHIJIAZHUANG UNIVERSITY
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