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Method for preparing o-trifluoromethyl phenylamine and derivatives thereof

A technology of trifluoromethylaniline and aniline derivatives, which is applied in the field of preparation of trifluoromethylaniline derivatives, can solve the problem of less trifluoromethylaniline, and achieve the effect of mild reaction conditions

Inactive Publication Date: 2014-02-05
NANJING UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, so far, there are few effective synthetic methods for directly introducing a trifluoromethyl group on an unprotected aromatic amine [see: (a) Hafner, A.; S.Angew.Chem.Int.Ed.2012,51,3713.(b)Zhang,L.-S.;Chen,K.;Chen,G.;Li,B.-J.;Luo,S.; Guo, Q.-Y.; Wei, J.-B.; Shi, Z.-J. Org. Lett. 2013, 15, 10. (c) Besset, T.; Schneider, C.; Cahard, D. Angew.Chem.Int.Ed.2012,51,5048.(d)Ji,Y.;Brueckl,T.;Baxter,R.D.;Fujiwara,Y.;Seiple,I.B.;Su,S.;Blackmond,D.G.;Baran , P.S.Proc.Natl.Acad.Sci.U.S.A.2011,108,14411.]

Method used

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  • Method for preparing o-trifluoromethyl phenylamine and derivatives thereof
  • Method for preparing o-trifluoromethyl phenylamine and derivatives thereof
  • Method for preparing o-trifluoromethyl phenylamine and derivatives thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0020] Under the protection of nitrogen or argon, 4-bromoaniline 0.4mmol, 0.2mmol, Ir(ppy) 3 (2 mg) and 1 ml of DMF were added to the reaction flask, and then irradiated with a blue LED light strip (7W) at room temperature until the trivalent iodine reagent was completely converted to complete the reaction. Add 10 mL of saturated Na 2 CO 3 aqueous solution, extracted 3 times with ethyl acetate, the organic layer was washed once with saturated brine, anhydrous Na 2 SO 4 Dry the organic layer. Column chromatography [200-300 mesh chromatography silica gel (the same below), eluent: petroleum ether 60-90: ethyl acetate = 20:1-10:1], to obtain the product Yield 61% (86% NMR yield). 1 H NMR (400MHz, CDCl 3 ):δ(ppm)=7.53(d,J=2.0Hz,1H),7.37(dd,J=8.8,2.0Hz,1H),6.63(d,J=8.0Hz,1H),3.86(s,2H ); 13 C NMR (100MHz, CDCl 3 ):δ(ppm)=143.5,135.6,129.2(q,J=5.5Hz),124.0(q,J=270.7Hz),110.8,115.2(q,J=30.9Hz); 19 F NMR (376MHz, CDCl 3 ):δ(ppm)=-63.2; HRMS(ESI)m / z calcd for C 7 h 4 B...

Embodiment 2

[0022] Under the protection of nitrogen or argon, 4-iodoaniline 0.4mmol, 0.2mmol, Ir(ppy) 3 (2 mg) and 1 ml of DMF were added to the reaction flask, and then irradiated with a blue LED light strip (7W) at room temperature until the trivalent iodine reagent was completely converted to complete the reaction. Add 10 mL of saturated Na 2 CO 3 aqueous solution, extracted 3 times with ethyl acetate, the organic layer was washed once with saturated brine, anhydrous Na 2 SO 4 Dry the organic layer. Column chromatography (eluent: petroleum ether 60-90: ethyl acetate = 20:1-10:1) to obtain the product Yield 60%. 1 H NMR (400MHz, CDCl 3 ):δ(ppm)=7.68(d,J=1.6Hz,1H),7.52(dd,J=8.4,1.6Hz,1H),6.51(d,J=8.4Hz,1H),3.98(s,2H ); 13 C NMR (100MHz, CDCl 3 ):δ(ppm)=144.1,141.4,134.9(q,J=5.4Hz),123.8(q,J=271.3Hz),119.2,115.7(q,J=30.8Hz),77.4; 19 F NMR (376MHz, CDCl 3 ):δ(ppm)=-63.2; HRMS(ESI)m / z calcd for C 7 h 4 f 3 IN[M-H] - :285.9346;found:285.9341.

Embodiment 3

[0024] Under the protection of nitrogen or argon, 0.4mmol, 0.2mmol, Ir(ppy) 3 (2 mg) and 1 ml of DMF were added to the reaction flask, and then irradiated with a blue LED light strip (7W) at room temperature until the trivalent iodine reagent was completely converted to complete the reaction. Add 10 mL of saturated Na 2 CO 3 aqueous solution, extracted three times with ethyl acetate, washed once with saturated brine, anhydrous Na 2 SO 4 Dry the organic layer. Column chromatography (eluent: petroleum ether 60-90: ethyl acetate = 15:1-8:1) to obtain the product Yield 67%. 1 H NMR (400MHz, CDCl 3 ):δ(ppm)=8.14(d,J=1.6Hz,1H),7.95(dd,J=8.4,1.6Hz,1H),6.73(d,J=8.4Hz),4.31(s,2H), 3.88(s,3H); 13 C NMR (100MHz, CDCl 3 ):δ(ppm)=166.2,148.3(d,J=1.8Hz),134.3,129.2(q,J=4.8Hz),124.5(q,J=271.2Hz),119.1,116.3,112.7(q,J =30.8Hz),51.9; 19 F NMR (376MHz, CDCl 3 ):δ(ppm)=-63.1; HRMS(ESI)m / z calcd for C 9 h 7 f 3 NO 2 [M-H] - :218.0434;found:218.0449.

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Abstract

The invention discloses a method for preparing o-trifluoromethyl phenylamine and derivatives thereof. According to the method, phenylamine or a phenylamine derivative serving as raw material reacts with a trivalent iodine reagent compound 2 in a solution under the protection of argon or nitrogen and illumination condition in the presence of tri(2-phenylpyridine)-iridium [Ir(ppy)3] serving as a catalyst to produce o-trifluorophenylamine or derivatives thereof 3, wherein the trivalent iodine reagent compound 2 has a structure shown in the specification. The method is mild in reaction conditions, the amino does not need to be protected, and trifluoromethyl substituted phenylamine or phenylamine derivatives can be directly obtained.

Description

technical field [0001] The invention relates to a preparation method of trifluoromethylaniline derivatives. Background technique [0002] Studies in recent years have shown that introducing a trifluoromethyl group into an important molecular skeleton can significantly improve its chemical properties and bioavailability, further enhance its biological activity, and has a good application prospect [see: (a) Shimizu, M. ; P.R.; Swallow, S.; Gouverneur, V. Chem. Soc. Rev. 2008, 37, 320.]. As an important pharmaceutical chemical raw material, aniline is widely used in the fields of dyes, fine chemicals and pharmaceuticals. However, so far, there are few effective synthetic methods for directly introducing a trifluoromethyl group on an unprotected aromatic amine [see: (a) Hafner, A.; S.Angew.Chem.Int.Ed.2012,51,3713.(b)Zhang,L.-S.;Chen,K.;Chen,G.;Li,B.-J.;Luo,S.; Guo, Q.-Y.; Wei, J.-B.; Shi, Z.-J. Org. Lett. 2013, 15, 10. (c) Besset, T.; Schneider, C.; Cahard, D. Angew.Chem....

Claims

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Application Information

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IPC IPC(8): C07B37/04C07C211/52C07C209/74C07C229/60C07C227/16C07C225/22C07C221/00C07C237/30C07C231/12C07C217/84C07C213/08C07F5/04C07D213/38C07D249/08C07C323/36C07C319/20C07C311/08C07C303/40C07D311/58C07C317/36C07C315/04C07J41/00
Inventor 朱成建谢劲胥攀
Owner NANJING UNIV
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