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Metallofullerene nitroxide free radical derivative as well as preparation method and application thereof

A technology of fullerene nitroxide radical and metallofullerene, which can be used in the preparation of carbon-based compounds, the preparation of organic compounds, chemical instruments and methods, etc., and can solve the problems of complex catalyst components, poor selectivity, and peroxidation.

Active Publication Date: 2018-08-24
INST OF CHEM CHINESE ACAD OF SCI +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0007] In order to solve problems such as poor selectivity, overoxidation, the need for multiple functional catalysts to be used in conjunction with complex catalyst components, etc. in the process of oxidizing alcohol compounds into corresponding aldehydes or ketones in the prior art, the purpose of the present invention is to Provided are a metal fullerene nitroxide radical derivative and its preparation method, and the application of the metal fullerene nitroxide radical derivative in highly selective catalytic oxidation of alcohol compounds under visible light

Method used

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  • Metallofullerene nitroxide free radical derivative as well as preparation method and application thereof
  • Metallofullerene nitroxide free radical derivative as well as preparation method and application thereof
  • Metallofullerene nitroxide free radical derivative as well as preparation method and application thereof

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0055] Example 1 metal fullerene Sc 3 N@C 80 Preparation method of nitroxide free radical derivative

[0056] (1) The preparation method of DPP-carboxyl group,

[0057]

[0058] Including: take 50mg (ie 0.0672mmol) of DDP (ie R in formula 4 1 for-C 4 h 9 , the R 2 for-C 6 h 13 ), 22.3mg (ie 0.1344mmol) of 4-carboxyphenylboronic acid (ie R 3 For -H), 3.88mg (that is, 0.00336mmol) of 4-(triphenylphosphine) palladium as a catalyst, and 12.8mg (that is, 0.121mmol) of sodium carbonate that provide an alkaline environment are dissolved in 20ml of 1,4-diox In the mixture of six rings, 20ml of dichloromethane and 4ml of water, under magnetic stirring, use a double-row tube to degas three times, then raise the temperature to 110°C under an inert atmosphere of argon, and react overnight; the reaction is complete Finally, wash with 50ml of 0.1M hydrochloric acid aqueous solution, then wash with deionized water, and finally extract three times with 30ml of dichloromethane, com...

Embodiment 2

[0076] Metallofullerene Sc 3 N@C 80 The reaction of catalyzing the conversion of enol compounds by derivatives of nitroxide radicals is as follows:

[0077] Metal fullerene Sc obtained in embodiment 1 3 N@C 80 Nitroxide radical derivatives are mixed with different small molecule enol compounds (see the next paragraph for specific reaction conditions), irradiated under visible light conditions, stirred for a period of time, and detected by gas chromatography. The results show that for different kinds of enols, metallofullerene Sc 3 N@C 80 When the nitrogen oxide free radical derivative is used as the catalyst, the selectivity is very good, the double bonds of the olefins are not destroyed, and the conversion of alcohols to aldehydes has occurred.

[0078] Reaction conditions: 0.5mmol enol compound substrate, 5×10 -3 mmolerene metal Sc 3 N@C 80 Nitroxide radical derivatives are used as catalysts, 0.5mmol of n-octane is added as an internal standard, dissolved in 500μL of...

Embodiment 3

[0084] Metallofullerene Sc 3 N@C 80 The reaction of the conversion of polyhydric alcohols that derivatives of nitroxide radicals participate in is as follows:

[0085] As shown in the following reaction formula, for reaction (1), add metal fullerene Sc obtained in Example 1 3 N@C 80Nitroxide free radical derivatives react with the corresponding substrate, 1,5-hexanediol to generate 87% of 5-hydroxyhexanal and 12% of 6-hydroxyhexyl-2-one. The reaction system is as follows: 0.5mmol 1,5-Hexanediol, 5 x 10 -3 mmolerene metal Sc 3 N@C 80 Nitroxide radical derivatives were used as catalysts, 0.5 mmol of n-octane was added as an internal standard, dissolved in 500 μL of toluene, mixed thoroughly and exposed to visible light for 5 hours, and the obtained products were detected by gas chromatography.

[0086] For reaction (2) (1-(4-(hydroxymethyl) phenyl) ethanol reacts and generates about 78% 4-(1-hydroxyethyl-benzaldehyde), less than 2% of 1-(4-( Hydroxymethyl) phenyl) ethyl k...

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Abstract

An embodiment of the invention relates to a metallofullerene nitroxide free radical derivative as well as a preparation method and an application thereof. The metallofullerene nitroxide free radical derivative in the embodiment can efficiently produce electron transfer under irradiation of visible light, so that a NO free radical turns into NO+ with certain catalytic oxidation activity, and efficient and high-selectivity catalytic conversion of alcohol compounds into aldehyde compounds is realized under the mild condition. Meanwhile, the metallofullerene nitroxide free radical derivative catalyst can replace functions of multiple reported catalysts in a catalyst system taking the nitroxide free radical as one of catalysts; besides, the dose of the metallofullerene nitroxide free radical derivative catalyst is basically 1 / 10 of that of NO free radical catalysts in the prior art, but similar or better effects can be realized.

Description

technical field [0001] The present invention relates to the field of metallofullerene derivatives, and further relates to metallofullerene nitroxide radical derivatives and their preparation methods and applications, especially to metallofullerene nitroxide radical derivatives and their preparation methods and their use under visible light. Application of highly selective catalytic oxidation of alcohol compounds. Background technique [0002] In organic synthesis, the selective oxidation of alcohols to corresponding aldehydes or ketones is an important functional group reaction, which occupies a very important position in the field of basic research and fine chemical production. Worldwide production of carbonyl compounds by oxidation of alcohols exceeds one million tons per year. Traditionally, this transformation adopts the method of metered oxidation, and there are many kinds of oxidants used, such as: chromium reagent, manganese reagent and other transition metal oxides ...

Claims

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Application Information

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IPC IPC(8): C07D487/04C07C45/38C07C45/39B01J31/02C07C47/21C07C47/22C07C49/203C07C49/603
CPCB01J31/0254B01J31/0271B01J2231/763C07C45/38C07C45/39C07C2601/16C07D487/04C07C47/21C07C47/22C07C49/203C07C49/603
Inventor 王春儒吴波柴永强
Owner INST OF CHEM CHINESE ACAD OF SCI
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