Amines based on electron-rich fluoroaromatic hydrocarbons, and preparation method of amines

A technology for fluorinated aromatic hydrocarbons and aminates, which is applied in the field of chemistry and can solve problems such as residual trace metals and harsh reaction conditions for guiding groups.

Active Publication Date: 2019-10-01
HUAZHONG NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the former method usually requires special ligands, directing gro

Method used

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  • Amines based on electron-rich fluoroaromatic hydrocarbons, and preparation method of amines
  • Amines based on electron-rich fluoroaromatic hydrocarbons, and preparation method of amines
  • Amines based on electron-rich fluoroaromatic hydrocarbons, and preparation method of amines

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0028]

[0029] Under argon protection, add p-fluoroanisole a1 (0.0126g, 0.10mmol), acridine photosensitizer (A) (0.0029g, 0.005mmol) and L-valine ethyl ester b1 (0.0218g, 0.15mmol) ), 1,2-dichloroethane (DCE) 2.0mL. Placed under 6W blue light at room temperature to react for 48h. After the reaction, the solvent was distilled off under reduced pressure and separated by column chromatography, eluent: (V) petroleum ether / (V) ethyl acetate=20 / 1. A yellow liquid (1) (0.0208 g, 93%) was obtained.

[0030] 1 H NMR (400MHz, CDCl 3 ): δ6.77(d, J=7.6Hz, 2H), 6.62(d, J=7.6Hz, 2H), 4.17(q, J=6.4Hz, 2H), 3.87(s, 1H), 3.74(s ,3H),2.11-2.06(m,1H),1.25(t,J=6.8Hz,3H),1.05(d,J=6.8Hz,3H),1.03(d,J=6.4Hz,3H); 13 C NMR (100MHz, CDCl 3 ): δ174.0, 152.6, 141.5, 115.2, 114.8, 63.7, 60.7, 55.7, 31.5, 19.1, 18.7, 14.3; HRMS (ESI) m / z calcd for C 14 h 22 NO 3 (M+H) + 252.1594, found 252.1604.

Embodiment 2

[0032]

[0033] Under argon protection, p-fluoroanisole a1 (0.0126g, 0.10mmol), acridine photosensitizer (A) (0.0029g, 0.005mmol) and D-dimethyl aspartate b2 (0.0242g, 0.15mmol), 1,2-dichloroethane (DCE) 2.0 mL. The reaction was irradiated under 6W blue light for 48 h at room temperature. After the reaction was finished, the solvent was distilled off under reduced pressure, separated by column chromatography, eluent: (V) sherwood oil / (V) ethyl acetate=6 / 1. A yellow liquid (2) (0.0206 g, 87%) was obtained.

[0034] 1 H NMR (400MHz, CDCl 3 ): δ6.79(d, J=8.8Hz, 2H), 6.67(d, J=8.8Hz, 2H), 4.38(t, J=6.6Hz, 1H), 4.16(s, 1H), 3.74(s ,6H),3.70(s,3H),2.86(d,J=5.6Hz,2H); 13 C NMR (100MHz, CDCl 3 ): δ173.1, 171.0, 153.1, 140.2, 115.7, 114.8, 55.6, 54.8, 52.5, 52.0, 37.3; HRMS (ESI) m / z calcd for C 13 h 18 NO 5 (M+H) + 268.1180, found 268.1190.

Embodiment 3

[0036]

[0037] Under the protection of argon, add p-fluoroanisole a1 (0.0126g, 0.10mmol), acridine photosensitizer (A) (0.0029g, 0.005mmol) and L-phenylalanine methyl ester b3 (0.0269g, 0.15 mmol), 1,2-dichloroethane (DCE) 2.0 mL. The reaction was irradiated under 6W blue light for 48 h at room temperature. After the reaction, the solvent was distilled off under reduced pressure and separated by column chromatography, eluent: (V) petroleum ether / (V) ethyl acetate=10 / 1. A yellow liquid (3) (0.0237 g, 93%) was obtained.

[0038] 1 H NMR (400MHz, CDCl 3 ):δ7.23-7.20(m,2H),7.18-7.15(m,1H),7.10(d,J=6.8Hz,2H),6.69(d,J=8.0Hz,2H),6.50(d, J=7.6Hz, 2H), 4.22(t, J=6.0Hz, 1H), 3.65(s, 3H), 3.57(s, 3H), 3.04(d, J=6.6Hz, 2H); 13 C NMR (100MHz, CDCl 3 ): δ173.9, 152.7, 140.4, 136.4, 129.2, 128.5, 126.9, 115.2, 114.8, 58.9, 55.6, 52.0, 38.8; HRMS (ESI) m / z calcd for C 17 h 20 NO 3 (M+H) + 286.1438, found 286.1445.

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Abstract

The invention provides amines based on electron-rich fluoroaromatic hydrocarbons, and a preparation method of the amines. The structure of the amines is as shown in a formula I. The invention also provides the preparation method of the amines based on the electron-rich fluoroaromatic hydrocarbons; the method concretely comprises the following steps: dissolving a compound a in an organic solvent together with a photosensitizer and a compound b at the temperature of 25 DEG C under the protection of argon, irradiating with blue light for 48-72h, reducing pressure and distilling, carrying out column chromatography, and leaching to obtain the amines. The preparation method provided by the application utilizes a photoredox catalytic principle mediated by visible light; compared with the traditional method, the method is more environmentally-friendly, milder in conditions and more suitable for amination of the electron-rich fluoroaromatic hydrocarbons.

Description

technical field [0001] The present invention relates to the field of chemistry, specifically, the present invention relates to electron-rich fluorinated arene-based amides and preparation methods thereof. Background technique [0002] Fluorinated aromatic compounds are extremely precious molecules, which are widely used in the fields of medicine, pesticides, and material chemistry. The development of direct C-F bond activation methods is of great importance for the post-functional modification, structural modification, and synthetic transformation of such fluorides. significance. The construction of aromatic amines, which play an important role in the chemical industry, through the activation of C-F bonds has great development value. [0003] So far, many research groups have devoted themselves to the work in this area. On the one hand, a transition metal-catalyzed method has been developed to realize the cross-coupling reaction of fluorinated aromatic hydrocarbons and amin...

Claims

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Application Information

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IPC IPC(8): C07C229/18C07C227/18C07C229/24C07C229/36C07C229/22C07D209/20C07C229/48C07D211/58C07D223/16C07C217/84C07D333/20C07C213/02C07F7/18C07C233/43C07C231/12C07D205/08
CPCC07C229/18C07C229/24C07C229/36C07C229/22C07D209/20C07C229/48C07D211/58C07D223/16C07C217/84C07D333/20C07F7/1804C07C233/43C07D205/08
Inventor 周少林石维敏
Owner HUAZHONG NORMAL UNIV
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