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31.32.1.1.1 Variation 1: By Reaction with Halogens

DOI: 10.1055/sos-SD-031-01909

Chiara, J. L.Science of Synthesis, (2007311727.

The reaction of primary arylamines 8 with excess fluorine, using liquid hydrogen fluoride, acetonitrile, sulfuric acid, or acetic acid as solvent affords stable N,N-difluoroarylamines 9 in good yield (Scheme 3).[‌34‌,‌35‌] The choice of solvent depends on the nature of the starting arylamine. In general, acetonitrile is suitable where solubility of the arylamine presents no problem, while anhydrous hydrogen fluoride is preferable in cases where protonation of the amino group does not occur. The procedure only works satisfactorily with weakly basic nitro-substituted arylamines. Aniline and mononitroanilines give complex product mixtures under these reaction conditions.

Meeeee 8 Meeeeeeee ee M,M-Meeeeeeeeeeeeeeeee ee Meeeeeee ee Meeeeeeeee eeee Meeeeeee[‌88‌]

Meeeeeeeeee 8

M8 M8 M8 M8 Meee (°M) Meee Meeee (%) Mee
M MM8 M M 88 ee 8 88eee 88 [‌88‌]
M MM8 M MM8 8 ee 8 8e 88 [‌88‌]
M MM8 Me MM8 8 ee 8 88eee 88 [‌88‌]
M MM8 MMe MM8 8 ee 8 88eee 88 [‌88‌]
MM8 MM8 M MM8 88 8e 88 [‌88‌]

Mee eeeeeeee ee eeeeeeee eeee eeeeeee eeeeeeeeee eeeeee M-eeeeee- 88 ee M,M-eeeeeeeeeeeeeeeeee 88 eeeeeeeee ee eee eeeeeeeeeeeee ee eee eeeeeeeee (Meeeee 8).[‌88‌,‌88‌] Mee eeeeeeee ee eeeeeeeee eeeeeeeee ee eee eeeeeeeeeee eee ee eee eeeeeeee ee e eeee. Mee eeee ee eeee ee eeee eee eeeeeeee eeeeeeee eeeeee ee eee eeeeeeee, eeeee eee eeeeeeee eee eeeeeeeeeeeeee ee eee M-eeeeeeeeeee ee eeee-eeeeeeeeeee eeeeeeee. Meee eeeeee eeeee eeeeee eeeeeee eeee eeeeee eeeeeeee eeeeeeeeee (e.e., 8-eeeeeeeeeeeee 88) eeee eee ee eeeee eeeeee M-eeeeeeeeeeee eeeeeeee (e.e., eeeeeee eeeeeeeeeeee ee eeee-eeeee eeeeeeeeeeee; eee Meeeeee 88.88.8.8.8). Meeeeeeee eeeeee (>88%, eeeeeeeeee ee MM eeeeeeee eeeee eeeeeeeee ee eee eeeee eeeeeeee eeeeeee eeee eeeeeeee eeeeee) ee M-eeeeeeeeeeeeeee eeeeeeee eee eeeeeeee eeee eee eeeeeeee ee eeeeeeeee eeee e eeeeeeeeeeeeee eeeeee ee eeeeeeee ee eee eeeeeeee ee eee eeeeeee-eeeee eeeeeeeee eee(8-eeee-eeeee-8-eeeeeee-8-eeeeeeeeeeee) eeeeeee.[‌88‌] Meeeeeeee ee eee M,M-eeeeeeeeeee 88 eeee eeeeee eeeeeeee ee eeeeee eeee eeeeeee M,M-eeeeee-M-eeeeeeeeeee 88, eeeee ee eee eeeeeee ee eeeeeeeeeeee ee eeee eeeeeeee eee eeeeee (Meeeee 8).[‌88‌] Me eeee eeeee, eeeeeeee-ee-eeeeee eeeeeeeeeeeee ee eeeeeeee eeeeee ee eeeee eeeeeeeeee ee M-eeeeeeeeeeee.

Meeeee 8 Meeeeeeee ee M-Meeeeeeeeeeeeeee ee Meeeeeee ee Meeeeeeeee eeee Meeeeeee[‌88‌,‌88‌,‌88‌]

Meeee eee eeee e eee eeeeeee ee eee eeeeeeeeeee ee M-eeeeeeeeeeeeeee[‌88‌‌88‌] ee eeeeeeee ee eeeeeeeeee eeee eeeeeee, eee ee eeee eeeee eeee eeee-eeeeeeeeee eeeeeeee eee eeeeeeee eeee eee eeeeeeee.[‌88‌,‌88‌] Mee eeeeeeeeeee ee eee eeeeee eeeeeeee M-eeeeeeeeeeee ee eeeeeeee ee eee eeeeeee eeee ee eeeeeee eeee eeeeeee eee eeee eeeeeeee, eee ee eeeeeeeeeeee eeeeeee eee eeeee.[‌88‌] M-Meeeeeeeeeee eeee eeee eeeeeeee ee eeeeeeeee eeeeeeeeeeeee ee eee eeeeeeee ee eeeeeeee eeee eeeeee.[‌88‌]

Meeeeeeeeeee Meeeeeeee

M-Meeeee-8-eeeeeeeeeeeee 88; Meeeeee Meeeeeeee:[‌88‌]

M eeee ee e 8-eeeeeeeeeeee 88 (8.88eeee) ee MMe8 (88eM) (MMMMMMM: eeeee) eee eeeeeee eeee eee(8-eeee-eeeee-8-eeeeeee-8-eeeeeeeeeeee) eeeeeee (8ee) eee eeeee MeMMM8 (888ee). M 8.888M eeee ee Me8 ee MMe8 (8.8eM) eee eeeee ee eee eeeeeee eee eee eeeeeee eee eeeeeee eee eeeeeee eeeeeee. Meeeee eeee eeee eee eeeeeeee eee eeeeeeeee ee MM eeeeeeeeeeee (ee eeeeeeeeeeeee ee eee ν̃MM eeee ee 88888888ee8). M eeeeee ee eee M8 eee eeee eeeeee eeee eee eeeeeee eee 8eee ee eeeeee eee eeeeeeee Me8. Mee eeee eee eeee eeeeeeee eeeeeee e eeeeee eeee ee eeeeee e MMe8 eeee ee eee eeeeeee.

M,M-Meeeeeee-8-eeeeeeeeeeee (88, M8=M8=M8=M):[‌88‌]

M eeee ee 8-eeeeeeeeeeee (88, M8=M8=M8=M; 88ee, 8.888eeee) ee MMe8 (88eM) (MMMMMMM: eeeee) eee eeeeeee eeee eeeee MeMMM8 (8.8e). M 8.888M eeee ee Me8 ee MMe8 (88.8eM, 8.88eeee) eee eeeee ee eee eeeeeee eee eee eeeeeee eee eeeeeee eee 88eee. Me eeee eeeee eee MM eeeeeeee eee eeee e eeee eeeee ν̃MM eeee ee 8888ee8. M eeeeee ee eee M8 eee eeee eeeeee eeee eee eeeeeee eee 8eee ee eeeeee eee eeeeeeee Me8. Mee eeee eee eeee eeeeeeee eeeeeee e eeeeee eeee ee eeeeee e MMe8 eeee ee eee eeeeeee.

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