New method for generating methyl ketone by using palladium catalytic oxidized olefins

A technology for oxidizing alkenes and methyl ketones, applied in chemical instruments and methods, preparation of organic compounds, organic chemistry, etc., can solve the problems of difficult laboratory preparation and industrial application, expensive palladium ligands, harsh reaction conditions, etc. Achieve the effects of high substrate conversion rate and product yield, fast reaction speed and high reaction efficiency

Active Publication Date: 2013-05-22
ZHEJIANG UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0007] These methods all have different disadvantages, such as expensive palladium ligands used, difficult to prepare, harsh reaction conditions, and low conversion rates, making laboratory preparation and industrial application difficult.

Method used

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  • New method for generating methyl ketone by using palladium catalytic oxidized olefins
  • New method for generating methyl ketone by using palladium catalytic oxidized olefins
  • New method for generating methyl ketone by using palladium catalytic oxidized olefins

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0033] In a 100mL Schlenk tube equipped with magnetic stirring, the whole system is in an all-oxygen atmosphere by repeatedly pumping oxygen, and then adding p-methylstyrene (that is, R in structural formula (I) 3 is methyl, R 1 , R 2 , R 4 , R 5 All hydrogen) 1mmol, palladium acetate 0.02mmol, benzoquinone 0.1mmol, sodium nitrite 0.2mmol, quickly add 5.0mL solvent (methanol: water = 4:0.5 (v / v)) and perchloric acid 0.4mmol, and then immediately The whole system was sealed in an oxygen atmosphere, and reacted at room temperature for 5 hours. After the reaction was completed, the solution was rotary evaporated, and the residue was purified with a silica gel column (eluent, petroleum ether: ethyl acetate = 10:1) to obtain the target product pair Methyl acetophenone, the yield is 91%. 1 H NMR (500MHz, CDCl 3 ):δ2.62(s,3H),7.47(t,J=7.5Hz,2H),7.58(t,J=7.0Hz,1H),7.97(t,J=4.5Hz,2H). 13 C NMR (125MHz, CDCl 3 ): δ26.5, 128.2, 128.5, 133.0, 137.1, 198.1.

Embodiment 2

[0035] The reactant used is p-bromostyrene (i.e. R in the structural formula (I) 3 is bromine, R 1 , R 2 , R 4 , R 5 Both are hydrogen), the experimental method and steps are the same as in Example 1, add solvent 5.0mL (acetonitrile: water = 5:0.5 (v / v)) and hydrochloric acid 0.3mmol, catalyst palladium acetate consumption is 0.05mmol, benzoquinone 0.1mmol, Sodium nitrite 0.2mmol, the reaction temperature is 30°C, the reaction time is 24h, and the yield is 85%. 1H NMR (500MHz, CDCl 3 ):δ2.60(s,3H),7.61-7.63(q,2H),7.83-7.84(q,2H). 13 C NMR (125MHz, CDCl 3 ): δ26.5, 128.4, 129.8, 131.9, 135.8, 197.1.

Embodiment 3

[0037] The reactant used is o-chlorostyrene (i.e. R in the structural formula (I) 1 is chlorine, R 3 , R 2 , R 4 , R 5 Both are hydrogen), the experimental method and steps are the same as in Example 1, add solvent 5.0mL (dichloromethane: water = 5:0.5 (v / v)) and acetic acid 0.3mmol, catalyst palladium acetate consumption is 0.05mmol, benzoquinone 0.1 mmol, 0.2 mmol of sodium nitrite, the reaction temperature is 25° C., the reaction time is 5 h, and the yield is 87%. 1 H NMR (500MHz, CDCl 3 ): δ2.64(s,3H),7.28-7.33(q,1H),7.36-7.42(q,2H),7.53-7.55(q,1H). 13 C NMR (125MHz, CDCl 3 ): δ30.7, 126.9, 129.4, 130.6, 131.3, 132.0, 139.1, 200.4.

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Abstract

The invention discloses a new method for generating methyl ketone by using palladium catalytic oxidized olefins. The method comprises the following step that: through taking an olefin compound as a raw material, taking air or oxygen as an oxidant, taking palladium acetate as a catalyst, taking benzoquinone and sodium nitrite as cocatalysts, and taking an acid as an initiator, the components are completely reacted in a reaction solvent so as to obtain a methyl ketone compound shown in formula (IV), (V) or (VI), wherein the structure of the olefin compound is shown in formula (I), (II) or (III). The method disclosed by the invention is mild in reaction conditions, high in efficiency and selectivity, and environment-friendly.

Description

(1) Technical field [0001] The invention relates to a method for palladium-catalyzed oxidation of alkenes to generate methyl ketone. (2) Background technology [0002] Palladium catalyst catalyzed oxidation of alkenes to carbonyl compounds is usually called Wacker oxidation reaction. In the history of the chemical industry, the Wacker oxidation reaction is the first reaction in which palladium catalysts are applied to the industrial production of organic synthesis, which has very important historical significance. Wacker oxidation has the advantages of mild reaction conditions, good substrate selectivity, and wide application range. Therefore, olefins can be used as potential functional groups of ketones in the design of organic synthesis routes. [0003] In the Wacker oxidation reaction, a certain amount of reoxidant is required to oxidize the metal palladium Pd(0) to generate Pd(II) during the reaction, so that the reaction can continue. The commonly used oxidant mainly i...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07B41/06C07C45/36C07C45/34C07C49/76C07C49/807C07C49/84C07C67/29C07C69/157C07C49/80C07C49/78C07C49/403C07C49/395C07C49/04
Inventor 张国富谢晓强丁成荣王涌温馨赵云
Owner ZHEJIANG UNIV OF TECH
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