Triethylamine → 3-Amino-5-fluorobenzotrifluoride

2-Bromo-5-fluoro-1-nitro-3-trifluoromethyl-benzene (XVIII) (55.5 g) is dissolved in 500 mL of ethanol. Triethylamine (19.63 g) and palladium on charcoal (6 g, Pd/C 10%, Engelhard 4505) are added and the mixture is subjected to hydrogenation at 20-25° C. After 20 hours reaction time, the consumption of hydrogen had ceased. The hydrogen pressure is released and the solution is separated from the catalyst by filtration on Cellflock. The filter residue comprising the catalyst is washed with ethanol (2×100 mL). The filtrate and wash fractions are combined and the solution thus obtained is concentrated at 45° C. under reduced pressure to a final volume of ca. 400 mL. Toluene (400 mL) is added and the resulting solution is concentrated to a final volume of ca. 250 mL to obtain a suspension. The precipitate is removed by filtration and the filter cake is washed with toluene (2×100 mL). The solution is concentrated again to a final volume of 200 mL and the formed precipitate is removed again by filtration. The filter cake is washed with toluene (3×50 mL). The process of dilution with toluene, concentration and filtration is repeated until no substantial precipitation occurred in the toluene solution. Finally, the solvent is evaporated at 45-50° C. under reduced pressure and the residue is dried in vacuo at 45° C. to obtain 3-fluoro-5-trifluoromethyl-phenylamine as a yellow oil. GC-MS: m/z: 179, 160, 151, 140, 132. The product is identical in GC and HPLC to a sample of 3-amino-5-fluoro-benzotrifluoride, purchased from ABCR (ABCR F01075). Also the NMR spectra are identical to the sample purchased from ABCR.

1. customis subjected to hydrogenation at 20-25° C
2. customAfter 20 hours reaction time
3. customthe consumption of hydrogen
4. customthe solution is separated from the catalyst by filtration on Cellflock
5. washis washed with ethanol (2×100 mL)
6. washThe filtrate and wash fractions
7. customthe solution thus obtained
8. concentrationis concentrated at 45° C. under reduced pressure to a final volume of ca. 400 mL
9. additionToluene (400 mL) is added
10. concentrationthe resulting solution is concentrated to a final volume of ca. 250 mL
11. customto obtain a suspension
12. customThe precipitate is removed by filtration
13. washthe filter cake is washed with toluene (2×100 mL)
14. concentrationThe solution is concentrated again to a final volume of 200 mL
15. customthe formed precipitate is removed again by filtration
16. washThe filter cake is washed with toluene (3×50 mL)
17. concentrationThe process of dilution with toluene, concentration and filtration
18. customis repeated until no substantial precipitation
19. customFinally, the solvent is evaporated at 45-50° C. under reduced pressure
20. customthe residue is dried in vacuo at 45° C.

ORD-Eintrag

ord-14f5a4b1590f488e9d2793b9043ded0d

Quelldatensatz

uspto-grants-2011_08

DOI

10.6084/m9.figshare.5104873.v1

Patentnummer

US08008504B2