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Copper-catalyzed method for preparing aldehyde or ketone compound by oxidizing alcohol with oxygen as oxidizing agent and application

A technology of ketone compounds and oxidants, applied in the preparation of organic compounds, compounds of group 4/14 elements of the periodic table, silicon organic compounds, etc., can solve the problem of limited types of catalytic substrates, use of high temperature and pressure, harsh reaction conditions, etc. problems, to achieve the effect of environmental friendliness, no pollution, high yield, and mild reaction conditions

Inactive Publication Date: 2020-08-04
FUDAN UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0003] The invention overcomes the defects of using heavy metals as catalysts or chlorides, harsh reaction conditions, long reaction time, limited types of catalytic substrates, high temperature and high pressure in the existing metal-catalyzed oxygen oxidation technology, and provides a A method of generating aldehydes or ketones by oxidation with oxygen under certain conditions, using copper salts and nitroxide radicals as catalysts, and oxygen as an oxidant

Method used

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  • Copper-catalyzed method for preparing aldehyde or ketone compound by oxidizing alcohol with oxygen as oxidizing agent and application
  • Copper-catalyzed method for preparing aldehyde or ketone compound by oxidizing alcohol with oxygen as oxidizing agent and application
  • Copper-catalyzed method for preparing aldehyde or ketone compound by oxidizing alcohol with oxygen as oxidizing agent and application

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Experimental program
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Embodiment 1

[0029]

[0030] Insert an oxygen balloon into the dry reaction tube, pump and exchange air three times, and add Cu(NO 3 ) 2 ·3H 2 O (24.6 mg, 0.1 mmol), TEMPO (16.2 mg, 0.1 mmol), 1b (146.4 mg, 1.0 mmol) in MeCN (4 mL). The reaction tube was stirred at 25°C for 6 hours. The reaction solution was filtered through a short column of silica gel (2 cm), washed with ether, and the solvent was removed by rotary evaporation. Separation and purification were carried out by silica gel column chromatography (eluent: petroleum ether / diethyl ether=60 / 1) to obtain product 2b (130.7 mg, 91%): white solid. Melting point: 44.2-44.7°C (petroleum ether / ethyl acetate recrystallization); 1 H NMR (400MHz, CDCl 3 ):δ=8.06(d,J=8.4Hz,2H,ArH),7.29(d,J=8.0Hz,2H,ArH),3.40(s,3H,CH 3 ),2.44(s,1H,≡CH); 13 C NMR (100MHz, CDCl 3 ): δ=177.0, 145.7, 133.8, 129.8, 129.4, 80.34, 80.28, 21.8; MS (70eV, EI) m / z (%): 144 (M + ,74.75),115(100);IR(neat):ν=3257,2090,1632,1594,1459,1404,1310,1246,1167,1117cm...

Embodiment 2

[0032]

[0033] Operation is with embodiment (1). Cu(NO 3 ) 2 ·3H 2 O (24.0mg, 0.1mmol), TEMPO (16.1mg, 0.1mmol), 1c (161.8mg, 1.0mmol), MeCN (4mL), reacted for 12.5 hours to obtain 2c (134.0mg, 84%) (eluent: petroleum Ether / ethyl acetate=30 / 1): oily liquid; 1 H NMR (400MHz, CDCl 3 ):δ=8.06(dd,J 1 =7.8Hz,J 2 =1.8Hz,1H,ArH),7.55(td,J 1 =8.0Hz,J 2 =1.8Hz,1H,ArH),7.07-6.97(m,2H,ArH),3.94(s,3H,CH 3 ),3.37(s,1H,≡CH); 13 C NMR (100MHz, CDCl 3 ): δ=175.8,159.8,135.4,132.9,125.5,120.1,112.0,81.9,79.5,55.6; MS(70eV,EI)m / z(%):161(M + +1,7.26),160(M + ,64.37),131(100);IR(neat):ν=3234,2089,1647,1595,1573,1484,1462,1434,1286,1253,1224,1164,1116,1019cm -1 .

Embodiment 3

[0035]

[0036] Operation is with embodiment (1). Cu(NO 3 ) 2 ·3H2 O (24.1mg, 0.1mmol), TEMPO (16.3mg, 0.1mmol), 1d (162.2mg, 1.0mmol), MeCN (4mL), reacted for 13 hours to give 2d (142.6mg, 89%) (eluent: petroleum Ether / ethyl acetate=30 / 1): oily liquid; 1 H NMR (400MHz, CDCl 3 ):δ=7.80(d,J=7.6Hz,1H,ArH),7.64(s,1H,ArH),7.42(t,J=8.0Hz,1H,ArH),7.19(dd,J 1 =8.4Hz,J 2 =2.0Hz,1H,ArH),3.87(s,3H,CH 3 ),3.43(s,1H,≡CH); 13 C NMR (100MHz, CDCl 3 ): δ=177.1, 159.8, 137.4, 129.7, 122.9, 121.4, 112.8, 80.6, 80.3, 55.4; MS (70eV, EI) m / z (%): 161 (M + +1,11.54),160(M + ,100);IR(neat):ν=3250,2094,1644,1595,1581,1485,1429,1323,1264,1207,1177,1021,1012cm -1 .

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Abstract

The invention discloses a copper-catalyzed method for preparing an aldehyde or ketone compound by oxidizing alcohol with oxygen as an oxidizing agent. Reaction is performed in an organic solvent for 4-48 hours at room temperature by using copper salt and nitroxide free radicals as catalysts and oxygen or air as an oxidizing agent to efficiently oxidize an alcohol compound into the corresponding aldehyde or ketone compound. The method is simple to operate, free of chlorides corrosive to equipment, available in raw materials and reagents, mild in reaction conditions, wide in substrate universality, good in functional group compatibility, convenient in separation and purification, environmentally friendly in the whole process and free of pollution, and is a method suitable for industrial production.

Description

technical field [0001] The invention belongs to the technical field of chemical synthesis, and relates to a copper-catalyzed method and application for preparing corresponding aldehyde or ketone compounds by oxidizing alcohol with oxygen as an oxidant. Background technique [0002] As an important class of raw materials for organic synthesis, aldehydes and ketones are widely used in the production and research of chemicals. Oxidation reaction is one of the most basic and important types of chemical reactions. In industry, aldehydes and ketones are often prepared by oxidizing alcohols. Therefore, the development of a mild, environmentally friendly, efficient and convenient catalytic oxidation system has broad application prospects. The traditional oxidation method of alcohols often needs to use equivalent oxidants and produce equivalent industrial waste, which brings great harm to the ecological environment and is not suitable for large-scale industrial production (ChromiumO...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C49/794C07C49/84C07C45/39C07C69/78C07C67/313C07D333/22C07C49/207C07C49/798C07C49/796C07F7/08C07C49/807C07C49/835C07C255/56C07C253/30C07C205/45C07C201/12C07D307/46C07C49/255C07C47/21C07C47/55C07C47/225
CPCC07C49/794C07C49/84C07C69/78C07D333/22C07C49/207C07C49/798C07C49/796C07C49/807C07C49/835C07C255/56C07C205/45C07D307/46C07C49/255C07C47/21C07C47/55C07C47/225C07C2601/02C07C2601/14C07C67/313C07C45/39C07C201/12C07C253/30C07C45/38C07F7/083C07B41/06B01J31/28B01J31/006B01J2231/763C07C69/76C07C49/563C07C47/24C07C47/277C07C47/02C07C49/04
Inventor 麻生明翟迪
Owner FUDAN UNIV