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Method for preparing fluoroalkylarylamine by coupling aromatic boronic acid and fluoroalkylamine

A technology of fluoroalkylarylamine and fluoroalkylamine, which is applied in the field of preparation of fluoroalkylarylamine, can solve the problems that the oxidative cross-coupling of arylboronic acid and trifluoroethylamine has not been reported yet, and achieve the reaction Easy to operate and well tolerated

Active Publication Date: 2022-05-20
JIANGXI NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although many different types of amines have been successfully used in the Chan-Lam-Evans reaction, to the best of our knowledge, the Cu-mediated / catalyzed oxidative cross-coupling of arylboronic acids with trifluoroethylamine has not been reported

Method used

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  • Method for preparing fluoroalkylarylamine by coupling aromatic boronic acid and fluoroalkylamine
  • Method for preparing fluoroalkylarylamine by coupling aromatic boronic acid and fluoroalkylamine
  • Method for preparing fluoroalkylarylamine by coupling aromatic boronic acid and fluoroalkylamine

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025]

[0026] Add 4-phenylphenylboronic acid (0.25mmol), copper acetate (20mol%), stirring bar into a clean reaction tube, then plug the nozzle with a soft rubber stopper, then add triethylamine (0.75mmol), diethylamine (0.75mmol) and Fluoroethylamine (0.5mmol), dry acetonitrile (2.5ml), put the reaction tube in a heating module at 80°C, react overnight, and detect by TLC spot plate; after the reaction is completed, pad a layer of diatomaceous earth for suction filtration , and finally rinse diatomaceous earth several times with an organic solvent, add silica gel to spin dry the solvent, and separate by column chromatography to obtain the target compound, a white solid, with a yield of 81%.

[0027] 1 H NMR (400MHz, CDCl 3 )δ7.58–7.50(m,2H),7.45(J=8.6Hz,2H),7.39(t,J=7.7Hz,2H),7.30–7.24(m,1H),6.71(d,J=8.6 Hz, 2H), 5.92(tt, J=56.2, 4.4Hz, 1H), 3.92(s, 1H), 3.55(tdd, J=14.3, 6.6, 4.2Hz, 2H); 13 C NMR (100MHz, CDCl 3 )δ146.2, 140.9, 131.7, 128.7, 128.2, 126.4, 126.4, 114....

Embodiment 2

[0029]

[0030] In a clean reaction tube, add 4-tert-butylphenylboronic acid (0.25mmol), copper acetate (20mol%), stirring bar, then plug the nozzle with a soft rubber stopper, then add triethylamine (0.75mmol), Difluoroethylamine (0.5mmol), dry acetonitrile (2.5ml), the reaction tube was placed in a heating module at 80°C, reacted overnight, and detected by TLC spot plate; After filtration, diatomaceous earth should be rinsed several times with organic solvent, adding silica gel to spin dry the solvent, and separated by column chromatography to obtain the target compound as a light yellow liquid with a yield of 86%.

[0031] 1 H NMR (400MHz, CDCl 3 )δ7.23(d, J=8.7Hz, 2H), 6.60(d, J=8.7Hz, 2H), 5.88(tt, J=56.1, 4.2Hz, 1H), 3.76(s, 1H), 3.49( td,J=14.3,4.3Hz,2H),1.28(s,9H); 13 C NMR (100MHz, CDCl 3 )δ144.4, 141.6, 126.3, 114.7 (t, J = 241.8Hz), 112.9, 46.8 (t, J = 26.2Hz), 34.0, 31.6; 19 F NMR (376MHz, CDCl 3 )δ-122.57 (dt, J=56.3, 14.3Hz, 2F); 19 F { 1 H}NMR (376MHz,...

Embodiment 3

[0033]

[0034] In a clean reaction tube, add phenylboronic acid (0.25mmol), copper acetate (20mol%), stirring bar, then plug the pipe mouth with a soft rubber stopper, then add triethylamine (0.75mmol), difluoroethylamine ( 0.5mmol), dry acetonitrile (2.5ml), put the reaction tube in a heating module at 80°C, react overnight, and detect by TLC spot plate; The organic solvent was rinsed with diatomaceous earth several times, and the solvent was spin-dried by adding silica gel, and separated by column chromatography to obtain the target compound as a light yellow liquid with a yield of 93%.

[0035] 1 H NMR (400MHz, CDCl 3 )δ7.21(dd, J=8.5,7.3Hz,2H),6.83–6.74(m,1H),6.66(m,2H),5.91(tt,J=56.1,4.0Hz,2H),3.85(s ,1H),3.53(tdd,J=14.4,6.7,4.3Hz,2H); 13 CNMR (100MHz, CDCl 3 )δ146.8, 129.5, 118.7, 114.5 (t, J = 241.2Hz), 113.1, 46.5 (t, J = 26.2Hz); 19 F NMR (376MHz, CDCl 3 )δ-122.67 (dt, J=56.0, 14.4Hz, 2F); 19 F{ 1 H}NMR (376MHz, CDCl 3 )δ-122.67(s,2F).

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Abstract

The invention discloses a method for preparing fluoroalkylarylamine. The method uses aromatic boric acid and fluoroalkylamine as raw materials, uses cheap copper salt as a catalyst, and adds a certain amount of triethylamine. Under the reaction in acetonitrile, various fluoroalkylarylamines can be obtained, and the reaction formula is (1). The present invention realizes a method for preparing aromatic fluorinated aromatic amines by using aromatic boric acid as a reaction substrate under the catalysis / assistance of copper salts, and through the construction of C-N bonds. The method is simple and feasible, and has broad application prospects.

Description

technical field [0001] The invention relates to the field of organic chemistry, in particular to a method for preparing fluoroalkylarylamine. Background technique [0002] Aniline is a structural component of a large and growing number of natural and non-natural bioactive compounds. Anilines linked to electron-withdrawing groups (EWGs) are more important in drug development than the corresponding parent molecules because aerobic or metabolic degradation (a common problem encountered with anilines) can be significantly mitigated by the introduction of EWGs. Among the various EWGs, 2,2,2-trifluoroethyl is very attractive because it usually confers better pharmacokinetic and pharmacodynamic properties on drug candidates, such as lipophilicity, membrane permeability and metabolic stability . [0003] Conventional methods for the synthesis of trifluoromethylated anilines include S N Ar reactions, reductive aminations and N-trifluoroethylations using hypervalent iodine reagents...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C209/22C07C213/08C07C221/00C07C227/08C07C253/30C07C211/52C07C255/58C07C211/48C07C225/22C07C217/94C07C217/84C07C229/60C07B37/04
CPCC07B37/04C07C209/22C07C213/08C07C221/00C07C227/08C07C253/30C07C211/52C07C255/58C07C211/48C07C225/22C07C217/94C07C217/84C07C229/60
Inventor 胡祥国王辉
Owner JIANGXI NORMAL UNIV