A kind of polyethylene glycol monomethyl ether immobilized fluorine-containing carboxylic acid catalyst and its preparation method and application

A technology of polyethylene glycol monomethyl ether and fluorine-containing carboxylic acid, which is applied to the preparation of carboxylate esters, chemical instruments and methods, and the preparation of organic compounds, and can solve the problems of unsuitable industrial production, troublesome recycling, and the price of pentafluorobenzoic acid. Expensive and other issues, to achieve the effect of novel structure and easy preparation

Inactive Publication Date: 2017-11-28
SHIJIAZHUANG UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

But the used 2,3,4,5,6-pentafluorobenzoic acid of this method is expensive, reclaims trouble, is not suitable for industrialized production

Method used

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  • A kind of polyethylene glycol monomethyl ether immobilized fluorine-containing carboxylic acid catalyst and its preparation method and application
  • A kind of polyethylene glycol monomethyl ether immobilized fluorine-containing carboxylic acid catalyst and its preparation method and application
  • A kind of polyethylene glycol monomethyl ether immobilized fluorine-containing carboxylic acid catalyst and its preparation method and application

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0024] Preparation of polyethylene glycol monomethyl ether immobilized fluorine-containing carboxylic acid catalyst (1).

[0025] The structure of the catalyst (1) is shown in the following formula:

[0026]

[0027] 2.80 g (0.01 moL) of 2,2,3,3-tetrafluoro-1,4-butanedioic acid monobenzyl ester was added to 11.8 g of SOCl 2 Add 5 drops of DMF, heat to reflux for 2h, evaporate SOCl under reduced pressure 2 , to obtain 2,2,3,3-tetrafluoro-1,4-butanedioic acid monobenzyl chloride.

[0028] N 2 Under protection, 30g (0.005moL) MeO-PEG-OH 6000 was dissolved in 50mL CH 2 Cl 2 In ice bath cooling, add 1.21g (0.012moL) Et 3 N, stirring, slowly drop 2.98g (0.01moL) 2,2,3,3-tetrafluoro-1,4-butanedioic acid monobenzyl chloride and 5mL CH 2 Cl 2 After the dropwise addition, it was naturally raised to room temperature, reacted for 24 hours, and evaporated 30mLCH 2 Cl 2 , under stirring, the remaining reaction solution was added to 200mL of anhydrous ether, settled for 30min, fi...

Embodiment 2

[0032] Preparation of polyethylene glycol monomethyl ether immobilized fluorine-containing carboxylic acid catalyst (2).

[0033] The structure of the catalyst (2) is shown in the following formula:

[0034]

[0035] Replace 2.80g (0.01moL) of 2,2,3,3-tetrafluoro- 1,4-Monobenzyl succinate, and other operations were the same as in Example 1 to prepare catalyst (2). The amount of carboxyl groups immobilized in the catalyst (2) is 0.72mmol / g.

Embodiment 3

[0037] Preparation of polyethylene glycol monomethyl ether immobilized fluorine-containing carboxylic acid catalyst (3).

[0038] The structure of the catalyst (3) is shown in the following formula:

[0039]

[0040] Replace 2.80 g (0.01 moL) of 2,2,3,3-tetrafluoro-1,4-butanedioic acid monobenzyl ester with 3.28 g (0.01 moL) of 2,3,5,6-tetrafluoroterephthalic acid monobenzyl ester Benzyl ester, replace 1.21g (0.012moL) Et with 0.95g (0.012moL) pyridine 3 N, other operations were the same as in Example 1 to prepare catalyst (3). The amount of carboxyl groups immobilized in the catalyst (3) is 0.70mmol / g.

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Abstract

The invention discloses a polyethylene glycol monomethyl ether immobilized fluorine-containing carboxylic acid catalyst (formula I), a preparation method and application thereof. In formula I, A is independently a C2-C12 saturated polyfluorinated or perfluorocarbon chain, a C2-C12 unsaturated polyfluorinated or perfluorocarbon chain, C6H3F, C6H2F2, C6HF3, C6F4. The preparation method of formula I comprises the following steps: a. fluorine-containing dicarboxylic acid monobenzyl ester (formula II) reacts with SOCl2 to prepare fluorine-containing dicarboxylic acid monobenzyl chloride (formula III); b. in the presence of alkali, Fluorine-containing dicarboxylic acid monobenzyl chloride (formula III) reacts with polyethylene glycol monomethyl ether to prepare polyethylene glycol monomethyl ether-supported fluorine-containing carboxylic acid ester (formula IV); c. polyethylene glycol The monomethyl ether-supported fluorine-containing carboxylic acid ester (formula IV) is hydrodebenzylated under the action of Pd-C to prepare polyethylene glycol monomethyl ether-immobilized fluorine-containing carboxylic acid catalyst (formula I). The catalyst is easy to prepare, the reaction catalyzed is a homogeneous reaction, the aftertreatment is simple, and the catalyst is easy to recover and recycle. The catalyst can be applied to Baeyer-Villiger oxidation reaction, the condition is mild, and the product yield is high.

Description

technical field [0001] The invention relates to the field of organic synthesis, in particular to a polyethylene glycol monomethyl ether immobilized fluorine-containing carboxylic acid catalyst and a preparation method and application thereof. Background technique [0002] Fluorine is the most electronegative element in the periodic table. After the hydrogen on the carbon atom is replaced by fluorine, the bond energy increases by 16.5kcal / mol. Since the covalent radius of the fluorine atom is 0.72 Å, which is slightly larger than that of the hydrogen atom, which is equivalent to half of the C-C bond length of 1.31 Å, the fluorine atom can well shield the carbon chain and maintain a high degree of stability. Therefore, it contains a large amount of C-F Bonding compounds have analog effect, fat permeation effect, electronic effect and hindering effect. [0003] Baeyer-Villiger oxidation is an important class of reactions that oxidize cyclic ketones or open-chain ketones to lac...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J31/06C07D309/30C07C69/157C07C69/63C07C67/475C08G65/332
CPCY02P20/584
Inventor 史兰香张冀男张宝华郭瑞霞刘斯婕
Owner SHIJIAZHUANG UNIVERSITY
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