A kind of preparation method of 2-oxazolinone derivative

A technology for oxazolinone and derivatives, which is applied in the field of preparation of 2-oxazolinone derivatives, can solve the problems of limited types of 2-oxazolinone derivatives, cumbersome synthesis steps, high price, etc. High pressure reaction equipment, the effect of improving reaction efficiency and reducing dosage

Active Publication Date: 2017-04-05
BEIJING INSTITUTE OF TECHNOLOGYGY
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  • Application Information

AI Technical Summary

Problems solved by technology

However, the method usually requires reaction conditions such as high temperature and high pressure, and the reaction raw materials need cumbersome synthesis steps and are expensive, and the types of 2-oxazolinone derivatives prepared are very limited
In 2008, Li Chaojun’s research group reported the synthesis of 2-oxazolinone derivatives through the four-component series reaction of cheap and easy-to-obtain terminal alkynes, aldehydes, primary amines, and carbon dioxide. However, the amount of catalyst used in the method is as high as 30 mol%. Limits its application to some extent (Yoo, W.-J.; Li, C.-J., AdvSynth Catal 2008, 350, 1503-1506)

Method used

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  • A kind of preparation method of 2-oxazolinone derivative
  • A kind of preparation method of 2-oxazolinone derivative
  • A kind of preparation method of 2-oxazolinone derivative

Examples

Experimental program
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Effect test

Embodiment 1

[0026] Add 20mL of 1-n-butylamine into a 50mL reaction tube, and introduce carbon dioxide gas into it at a flow rate of about 25mL / min. After 5min, a white solid is obtained, which is butylammonium butylcarbamate; in a 10mL reaction tube with magnetic stirring, Add 10 mg of catalyst CuI, 0.4 mL of solvent isopropanol, 2 mmol of phenylacetylene, 2 mmol of benzaldehyde, and 1 mmol of butylammonium butylcarbamate. After sealing the reaction tube, control the reaction temperature at 80°C and react for 18 hours under magnetic stirring. The final product was separated by column chromatography, and the yield of the final product was 84% ​​based on the molar amount of carbon dioxide as 100%.

[0027] The final product is identified by nuclear magnetic resonance, gas chromatography-mass spectrometry, and high-resolution mass spectrometry, and is a 2-oxazolinone derivative according to the present invention. The specific results are as follows:

[0028]

[0029] (Z)-5-benzylidene-3-b...

Embodiment 2

[0032] The terminal alkyne is 4-methylphenylacetylene, other test methods and conditions are the same as in Example 1, and the yield of the final product is 86%.

[0033] The final product is identified by nuclear magnetic resonance, gas chromatography-mass spectrometry, and high-resolution mass spectrometry, and is a 2-oxazolinone derivative according to the present invention. The specific results are as follows:

[0034]

[0035] (Z)-3-butyl-5-(4-methylbenzylidene)-4-phenyloxazolidin-2-one,

[0036]1 H NMR (CDCl 3 ,400MHz): δ=7.42-7.25(m,7H),7.11-7.09(m,2H),5.37(s,1H),5.21(s,1H),3.54-3.47(m,1H),2.85-2.80 (m,1H),2.31(s,3H),1.47-1.43(m,2H),1.31-1.25(m,2H),0.87(t,3H,J=7.4Hz); 13 C NMR (CDCl 3 ,100.6MHz): δ=155.1,146.9,137.4,136.7,130.6,129.3,129.2,129.1,128.2,127.8,104.4,63.8,41.6,28.9,21.2,19.8,13.6; HRMS(ESI):C 21 h 23 NO 2 Na for [M+Na] + calculated 344.1621, found 344.1666; EI-MS, m / z(%): 194.10(100), 321.20(49)[M + ].

Embodiment 3

[0038] The terminal alkyne is 4-methoxyphenylacetylene, other test methods and conditions are the same as in Example 1, and the yield of the final product is 81%.

[0039] The final product is identified by nuclear magnetic resonance, gas chromatography-mass spectrometry, and high-resolution mass spectrometry, and is a 2-oxazolinone derivative according to the present invention. The specific results are as follows:

[0040]

[0041] (Z)-3-butyl-5-(4-methoxybenzylidene)-4-phenyloxazolidin-2-one,

[0042] 1 H NMR (CDCl 3 ,400MHz): δ=7.59-7.57(m,1H),7.47-7.36(m,3H),7.33-7.31(m,2H),6.84-6.82(m,3H),5.36(s,1H),5.19 (s,1H),3.78(s,1H),3.52-3.46(m,1H),2.85-2.79(m,1H),1.46-1.43(m,2H),1.30-1.26(m,2H),0.87 (t,3H,J=7.8Hz); 13 C NMR (CDCl 3 , 100.6MHz): δ=158.4, 155.1, 145.9, 137.5, 133.0, 129.6, 129.2, 127.7, 126.2, 113.8, 104.0, 63.7, 55.2, 41.5, 28.9, 19.7, 13.6; HRMS(ESI): C 21 h 23 NO 3 Na for [M+Na] + calculated 360.1570, found 360.1587; EI-MS, m / z(%): 210.10(100), 337.20(...

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Abstract

The present invention relates to a 2-oxazolidinone derivative preparation method, belongs to the technical field of organic synthesis. The preparation method is as follows: introducing carbon dioxide into primary amine, to obtain ammonium carbamate salt; then mixing the ammonium carbamate salt with a catalyst, a solvent, terminal alkyne and aldehyde; sealing the materials and stirring the materials at 40-120 DEG C for 8-24 h; after completion of the reaction, performing silical gel column chromatography, to obtaining the 2-oxazolidinone derivative, wherein the catalyst is cuprous chloride, cuprous bromide, cuprous iodide, cuprous thiocyanate, copper trifluoromethane sulfonate, cuprous oxide, copper sulfate, copper nitrate, or copper acetate; and the solvent is methanol, ethanol, ethylene glycol, diethylene glycol, isopropanol or N,N-dimethylformamide. According to the preparation method, the carbon dioxide is used as a protection agent of the primary amine and meanwhile as a reactant, and therefore the amount of catalyst is greatly reduced, the reaction efficiency is improved, and the reaction is performed at the atmospheric pressure, so that no oxygen-free operation is needed, the reaction is simple and safe, and the raw materials are cheap and readily available.

Description

technical field [0001] The present invention relates to a kind of preparation method of 2-oxazolidinone (2-oxazolidinone) derivative, specifically, relate to a kind of carbon dioxide (CO 2 ) is fixed as a green synthesis method of 2-oxazolinone derivatives, belonging to the technical field of organic synthesis. Background technique [0002] Since modern times, due to the consumption of a large amount of fossil fuels by human activities, the continuous accumulation of carbon dioxide in the atmosphere has caused a series of environmental problems such as the greenhouse effect and sea level rise. Over the past few years, the fixation and resource utilization of carbon dioxide has attracted widespread attention. In organic synthesis, carbon dioxide can be used as a carboxyl (ester)-based reagent to synthesize high value-added chemicals (T.Sakakura, J.-C.Choi, H.Yasuda, etc.) , Chem.Rev., 2007, 107, 2365-2387; K.Huang, C.-L.Sun, Z.-J.Shi, Chem.Soc.Rev., 2011, 40, 2435-2452; S.N...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D263/38
CPCC07D263/38
Inventor 胡长文於兵程彬彬
Owner BEIJING INSTITUTE OF TECHNOLOGYGY
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