Aniline → 4-(Heptafluoropropan-2-yl)aniline

100 g (1.02 mol) of aniline, 230 g (1.12 mol) of 85% sodium hydrosulfite, and 35.1 g (0.100 mol) of tetrabutylammonium hydrogen sulfate were charged to a mixed solution of 1500 ml of t-butyl methyl ether and 1500 ml of water, and 94.7 g (1.12 mol) of sodium hydrogen carbonate was added thereto. 350 g (1.12 mol) of heptafluoroisopropyl iodide was added dropwise thereto at room temperature, followed by stirring at room temperature for 6 hours. After the liquid separation, the organic layer was washed with 1 M hydrochloric acid, water, and a saturated aqueous sodium hydrogen carbonate solution, and then dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure, and 500 ml of ethyl acetate was charged thereto. 255 g (1.02 mol) of a 4 M hydrogen chloride/ethyl acetate solution was added dropwise thereto, followed by stirring at room temperature for 30 minutes and at 5° C. for 1 hour. The precipitated solid was separated by filtration, and the solid was charged to 1000 ml of ethyl acetate, adjusted to pH 8 to 9 by the addition of 1000 ml of a saturated aqueous sodium hydrogen carbonate solution at 20° C. or lower, and subjected to liquid separation. The organic layer was dried over anhydrous sodium sulfate, and then the solvent was evaporated under reduced pressure to prepare 188 g (yield 71%) of a target compound.

1. additionwas added
2. customat room temperature
3. customAfter the liquid separation
4. washthe organic layer was washed with 1 M hydrochloric acid, water
5. dry with materiala saturated aqueous sodium hydrogen carbonate solution, and then dried over anhydrous sodium sulfate
6. customThe solvent was evaporated under reduced pressure, and 500 ml of ethyl acetate
7. additionwas charged
8. addition255 g (1.02 mol) of a 4 M hydrogen chloride/ethyl acetate solution was added dropwise
9. stirringby stirring at room temperature for 30 minutes and at 5° C. for 1 hour
10. customThe precipitated solid was separated by filtration
11. additionthe solid was charged to 1000 ml of ethyl acetate
12. additionadjusted to pH 8 to 9 by the addition of 1000 ml of a saturated aqueous sodium hydrogen carbonate solution at 20° C.
13. customlower, and subjected to liquid separation
14. dry with materialThe organic layer was dried over anhydrous sodium sulfate
15. customthe solvent was evaporated under reduced pressure

ORD record

ord-3a2c0e9ba472484baf132248f5f1036b

Source dataset

uspto-grants-2016_01

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US09237745B2