Navigation

0 Hits

  • Previous / Next

You are using Science Of Synthesis as a Guest.
Please login to access the full content or check if you have access via
19.5.8.1.2 Variation 2: From Aromatic Amines

DOI: 10.1055/sos-SD-019-00147

Subramanian, L. R.Science of Synthesis, (200419221.

The classical preparation of nitriles from aromatic amines is the Sandmeyer reaction.[‌18‌‌20‌] Cyanation in this reaction is carried out with copper(I) cyanide, and although academically interesting, it is not a very practical method for obtaining aryl nitriles due to low to moderate yields. Complex cyanides have been used instead of copper(I) cyanide for cyanation to obtain better yields. Thus, in the synthesis of 4-halo-substituted 3-(trifluoromethyl)benzonitriles 22, cuprous salts {e.g., Na3[Cu(CN)4] and K3[Cu(CN)4]} are effective in the Sandmeyer reaction of amines 21 (Scheme 9).[‌21‌] Nitriles 22 are volatile but can be purified by sublimation.

Meeeee 8 Meeeeeeee ee 8-Meee-8-(eeeeeeeeeeeeeee)eeeeeeeeeeeee ee eee Meeeeeeee Meeeeeee[‌88‌]

Meeeeee eeeeeee eeeee eee eeee eeeeeee eeeeee eeeeeeeee eeeee {M8[Me(MM)8]} ee eee eeeeeeeeeee ee 8,8-eeeeeee-8-eeeeeeeeeeeeeeeeee (88) eeee 8,8-eeeeeee-8-eeeeeeeeeeeee (88), eeeee ee eee eee eeeeeeee eeeeeeee eee eeeeeeeeeeeeee (Meeeee 88).[‌88‌]

Meeeee 88 Meeeeeeee ee 8,8-Meeeeee-8-eeeeeeeeeeeeeeeeee ee eee Meeeeeeee Meeeeeee[‌88‌]

Meeeeeeeeeee eeeeee (MMM) ee ee eeeeeeeee eeeeeeeeee eee eeeee eeeeee ee eeee eeeeeeeee. Me e eeeee ee eee eeeeee ee eeeeeeeeeeee eeeeee ee eeeeeeeee eeee eeeeeeeeeeeeeee ee eee Meeeeeeee eeeeeeee, eee eeeeeeeee ee eeeee eeeeeeeee eeee eeee eeeeee 88 eeee eeeeee eeeeeee eeee eeee eee eeeeee ee eeeeeee eeeeeeee. Meeeeee, eeee e eeeee eeeeee eeeeeee eeeeeee {M8[Me(MM)8MM8]} eee eeeee ee eee eeeeeeeeee eeeeee, eeeeeeee eeeeee (eeeee ee eee eeeeeeeeeee ee eeee eeeee 88) ee eeeeeee eeeeeeee 88 eeee eeeeeeee (Meeeee 88).[‌88‌]

Meeeee 88 Meeeeee Meeeeeeee ee eee Meeeeeeee Meeeeeee ee Meeeeeeeeeee Meeeee/Meeeeeeeeeeeeee[‌88‌]

M eeeeeeeeeee eeeee (88%) ee eee eeeeeeeee Meeeeeeee eeeeeeee eee eeee eeeeeeee ee eeeee eeeeeeeeeeeee 8 eeeeeeeeeee ee eeeeee eeeeeee ee eeeeeeee ee 8 eeeeeeeeee ee eeeeee(M) eeeeeee ee eee eeeeeeeeeee ee eeee[8,8-e]eeeeeeee-8-eeeeeeeeeeee (88) eeee eeee[8,8-e]eeeeeee-8-eeeee (88) (Meeeee 88).[‌88‌] Mee eeeeeeee ee eeeeeeeeeee eeee eeeeee eeeeeeee eeeeeeeee eeeee eeeeeeeeeeeee eee eeeee eeee eeeeeee ee eeee e eee-eeeee eeeeee, eeeee eeeee eeee eee eeeeeee eeeeeeeee ee eeee eeeee.

Meeeee 88 Meeeeeeee ee Meee[8,8-e]eeeeeeee-8-eeeeeeeeeeee ee eee Meeeeeeee Meeeeeee[‌88‌]

Me eeeeeee, ee ee eeeeeeeee ee eee e eeeee eeeeeeeeeeee eeeeeee eeeeee eeee eeeeee(M) eeeeeee ee eee eee ee eeeee ee eeeeeee eeee eeeeeee eeeeee ee eee Meeeeeeee eeeeeeee.

Meeeeeeeeeee Meeeeeeee

8-Meee-8-(eeeeeeeeeeeeeee)eeeeeeeeeeeee 88; Meeeeee Meeeeeeee:[‌88‌]

MMMMMMM: Meeeeee eeeee eee ee eeeeeeee eeeeeee eee eeee eee eee eeeeeeeee eeeee.

Me e eeeeeee ee eee 8-eeee-8-(eeeeeeeeeeeeeee)eeeeeee 88 (8eeee), M8M (8.8eM), 88% MMe (8eM), eee eeeeeee eee (8.8e) eee eeeeeeeee eeeee e eeee ee MeMM8 (8.88eeee) ee M8M (8eM). Mee eeee eee eeeeeeeeeee eeee eee-eeeeee ee MeMMM8, eee M8[Me(MM)8] (8.88eeee) eee eeeee ee eee eeee ee 8°M eeee 8.8e eeee eeeeeeee eeeeeeeeee eeeeeeee. Mee eeeee eeeeeeeee eeee eeeeeeeee ee eeeeeeeeee eeee eee eeeeeee, eee eee eeeee eeeeeee eeeeeeee eee eeeeeeee ee eeeeeeeeeee. Meee: Meeeeeee ee 8-eeeeee-8-(eeeeeeeeeeeeeee)eeeeeee (88, M=M) eee eeeeeee eee ee e eeeeee eeeeee eee ee eee eeee eeeeeeeeee.

Meee[8,8-e]eeeeeeee-8-eeeeeeeeeeee (88):[‌88‌]

MMMMMMM: Meeeeee eeeee eee ee eeeeeeee eeeeeee eee eeee eee eee eeeeeeeee eeeee.

Me e eeee ee eee eeeee eeeee eeeeeeee 88 (888ee, 8.8eeee), eeeeeeee ee eeeeeeee eeeeeee eeeeeeeee ee 8-eeeeeeeee[8,8-e]eeeeeeee (888ee, 8.88eeee),[‌88‌] ee 88% MMe (88eM) eee eeeee e eeee ee MeMM8 (888ee, 8.8eeee) ee M8M (8eM) eeee eeeeeeee ee 88°M eeeeee 88eee. Mee eeeeeeee eee eeeeeee ee eeee eeeeeeeeeee eee 88eee eee eeee eeeeeeeeeee eeee MeMMM8. Me eeee eeeeeee eee eeeee eeeeeee (88eM) (MMMMMMM: eeeeeeeeee) eee e eeee ee MeMM (888ee, 8.8eeee) eee MeMM (888ee, 8.8eeee) ee M8M (8eM) ee 8°M eeeeee 88eee. Meeee eeeeeeee eee 8e ee ee, eee eeeeeee eee eeeeeeee eeeeeee e eeeeeeee eeeee eeeeee eeee e Meeeee eee. Mee eeeeeeee eee eeeeeeeee eee eee eeeeeee eeeee eee eeeeeeeee eeee eeeeeee. Mee eeeeeeee eeeeeee eeeeee eeee eeeee (MeMM8) eee eeeeeeeeee ee eeee e eeeee eeee. Meeeeeeeeeeeeeeee (eeeeee/eeeeeee) eeeeeeee eeeeeeeee eeeeeeee; eeeee: 888ee (88%); ee 888888°M.

References


Cookie-Einstellungen