Synthesis method of (E)-4-aryl-3-butenonitrile compound

A synthesis method and compound technology are applied in the field of chemical organic synthesis to achieve the effects of simple reaction steps, wide substrate range and high yield

Active Publication Date: 2019-04-19
ANYANG NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

But so far, there is no report on the method of synthesizing 3-butenenitriles through the C-C bond coupling reaction of olefins and bromoacetonitrile

Method used

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  • Synthesis method of (E)-4-aryl-3-butenonitrile compound
  • Synthesis method of (E)-4-aryl-3-butenonitrile compound
  • Synthesis method of (E)-4-aryl-3-butenonitrile compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0021] First, put a stirring bar in a 35mL sealed tube, add 35μL styrene (0.3mmol), 1.0ml acetonitrile, 38μL bromoacetonitrile (0.60mmol), and add 5.4mg Phen (0.03 mmol), 5.7mgCuI (0.03mmol) and 91μL DBU (0.60mmol), seal the nozzle tightly with a cock, heat to 110°C, and stir for 1.5 hours. After the reaction, the system is cooled to room temperature, and 2ml of distilled water is added to the reaction system. Extracted with ethyl acetate, combined the organic phases, and distilled off the solvent of the organic phase under reduced pressure, and separated by silica gel column chromatography to obtain 37.8 mg of colorless liquid product 3a, with a yield of 88%. The reaction is shown in the following formula:

[0022]

[0023] Spectral analysis data:

[0024] 1 H NMR (400MHz; CDCl 3 ):δ=3.30(dd,J 1 =1.6Hz,J 2 =5.6Hz,2H),6.06(dt,J 1 =15.6,J 2 =5.6Hz, 1H), 6.75(d, J=15.6Hz, 1H), 7.27-7.39(m, 5H); 13 C NMR (100MHz, CDCl 3 ): δ=20.8, 116.7, 117.3, 126.5, 128.3, 128.7, 13...

Embodiment 2

[0026] First, put a stirring bar in a 35mL sealed tube, add 37μL 4-fluorostyrene (0.3mmol), 1.0ml acetonitrile, 38μL bromoacetonitrile (0.60mmol), and add 5.4mg Phen (0.03mmol), 5.7mg CuI (0.03mmol) and 91μL DBU (0.60mmol), seal the mouth of the tube tightly with a cock, heat to 110°C, stir for 1.5 hours, after the reaction is over, cool the system to room temperature, and pour into the reaction system Add 2ml of distilled water, extract with ethyl acetate, combine the organic phases, distill off the solvent of the organic phase under reduced pressure, and separate by silica gel column chromatography to obtain 44.0 mg of colorless liquid product 3b, with a yield of 91%. The reaction is shown in the following formula:

[0027]

[0028] Spectral analysis data:

[0029] 1 H NMR (400MHz; CDCl 3 ):δ=3.29(dd,J 1 =1.2Hz,J 2 =5.6Hz,2H),5.98(dt,J 1 =15.6,J 2 =5.6Hz, 1H), 6.71(d, J=15.6Hz, 1H), 7.03(t, J=8.8Hz, 2H), 7.34(dd, J 1 =5.6,J 2 =8.4Hz,2H); 13 C NMR (100MHz, CDCl ...

Embodiment 3

[0031]First, put a stirring bar in a 35mL sealed tube, add 40μL 4-methylstyrene (0.3mmol), 1.0ml acetonitrile, 38μL bromoacetonitrile (0.60mmol), and add 5.4 mg Phen (0.03mmol), 5.7mg CuI (0.03mmol) and 91μL DBU (0.60mmol), seal the nozzle tightly with a cock, heat to 110°C, and stir for 1.5 hours. 2ml of distilled water was added to the mixture, extracted with ethyl acetate, the organic phases were combined, the solvent of the organic phase was distilled off under reduced pressure, and 33.5mg of colorless liquid product 3c was obtained by silica gel column chromatography, with a yield of 71%. The reaction is shown in the following formula:

[0032]

[0033] Spectral analysis data:

[0034] 1 H NMR (400MHz; CDCl 3 ):δ=2.43(s,3H),3.27-3.28(m,2H),5.99(dt,J 1 =16.0,J 2 =5.6Hz,1H),6.69(d,J=15.6,1H),7.14(d,J=8.0,2H),7.26(d,J=8.0,2H); 13 C NMR (100MHz, CDCl 3 ): δ=20.7, 21.2, 115.6, 117.4, 126.3, 129.4, 132.8, 134.5, 138.2.

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Abstract

The invention belongs to the technical field of organic synthesis chemistry, and discloses a synthesis method of a (E)-4-aryl-3-butenonitrile compound. According to the method, under catalysis of copper iodide, a target compound is synthesized in one step through a coupling reaction of aryl olefins with bromoacetonitrile or iodoacetonitrile. The method has the advantages that the atomic economy ishigh, reaction steps are simple, raw materials are cheap and easy to obtain, the application range of a substrate is wide, and the method is suitable for synthesis of various (E)-4-aryl-3-butenonitrile compounds and suitable for industrial production.

Description

technical field [0001] The invention belongs to the technical field of chemical organic synthesis, and relates to a method for synthesizing (E)-4-aryl-3-butenenitrile compound through copper-catalyzed coupling reaction of aryl olefin and bromoacetonitrile through C-C bond. Background technique [0002] Nitrile compounds widely exist in natural products and pharmaceutical products (Kleemann, A.; Engel, J.; Kutscher, B.; Reichert, D. Pharmaceutical Substance: Synthesis, Patents, Applications, 4th ed.; Georg Thieme: Stuttgart, 2001.), at the same time, this type of compound is also a very important organic synthesis intermediate in drug synthesis, and can be used as a precursor for the synthesis of compounds such as aldehydes, amides, tetrazoles, amidines and carboxylic acids ((a) Rappoport Z.The Chemistry of the Cyano Group, ed, Interscience, London, 1970; (b) Larock, R.C. Comprehensive Organic Transformations: A Guide to Fucntional Group Preparations, VCH, New York, 1989.). ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C253/30C07C255/34C07C255/35
CPCC07B2200/09C07C253/30C07C255/34C07C255/35
Inventor 吕允贺蒲卫亚孙凯李刚
Owner ANYANG NORMAL UNIV
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