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19.5.5.3.1 Variation 1: Using Copper(I) Cyanide

DOI: 10.1055/sos-SD-019-00127

Subramanian, L. R.Science of Synthesis, (200419180.

This method for the preparation of aryl cyanides was first reported in 1919[‌32‌,‌33‌] and is known as the Rosenmundvon Braun reaction. This is an important and useful method for the preparation of aromatic cyanides[‌34‌] and is usually carried out at elevated temperatures in nonpolar aprotic solvents, and thus has some limitations. The workup procedure is not simple, requiring the oxidation of copper(I) to copper(II) due to the complexation of aromatic cyanides with the copper(I) salt present in the reaction solution. Notwithstanding this fact, the Rosenmundvon Braun reaction is the method of choice for the preparation of phthalonitriles requiring the replacement of two halogen atoms and, except for one example based on bis(trifluoromethanesulfonates), there is no known alternative.

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Mee-eeeeeeeeeee eeeeee(M) eeeeeee[‌88‌] ee eeeeee eeee ee Meeeeeeeeeee Meeee eeeeeeee, eeeee ee eeeeeee eee eeeeeeeeeeeee ee eeeeeeee ee eeeeeeeee, eee eeeeeeeeee ee eeeeeeeeeeeeeeeee ee 8-eeeeeeeeeeeeeeee-8-eee. Meeeee eee eeeeeee. Mee eee ee eeeee eeeeeee ee eeeeeeee eee ee eeeeeee eeeeee, eee eeeeeeee eeeeee eeeee eeeee eeeeeeee ee eeee.[‌88‌] Mee eeeeee eeeeeeeeeeee eeeeeeee eee ee eeeeeeeeeee ee eee eee ee eeeeeeeee eeeeeee,[‌88‌] eee eee eeeeeee ee eeeeeee eeeeeeeee eeeeeee. Meeeeeee, eeeeeeeee-eeeeeeee eeeeeeeee ee eeee eeeeeee 88 ee eeee eeeeeeee 88 eeee eeeeee(M) eeeeeee ee e eeeeeee ee eeeeee eeeeeee eee eeeeee(M) eeeeee ee eee eeeeeeee ee eeeeeeeeeeeeeeeeee eeeeeee ee eeeee eee eeee eeeeeeee (Meeeee 88).[‌88‌] Mee eeeeeeee ee eee eeeee 888-M eeeeeeeee eeeee eee ee e eeeeeeeeeee eeeeeeeee ee 888°M eee 88eee.

Meeeee 88 Meeeeeeeeeee ee Meeeee ee Meee Meeeeee eeee Meeeee(M) Meeeeee ee Meeee eeeee Meeeeeeee Meeeeeeeee[‌88‌]

Meee eeeeeeee eeeeeeee ee eee eeeeee(M) eeeeeee eeeeeeeee ee eeeeeeee eeeeeee ee eeee eeeeeeee (e.e., 8888 eee 8888) eeee eee eeee eeeeee eeeeeeeeee eee eeeee ee Meeee 8.[‌88‌‌88‌]

Meeee 8 Meeeeeee ee Meee Meeeeeee Meeeeeee ee eee Meeeeeeeeeee Meeee Meeeeeee[‌88‌‌88‌]

Meee Meeeee Meeeeeee Meeeeeeeee Meee Meeeeee Meeee (%) Mee
MeMM, MMM, eeeeee, 88e 88 [‌88‌]
MeMM, MMM, 888°M, 88e 88 [‌88‌]
MeMM, MMM, 888°M, 88e 88 [‌88‌]
MeMM, MMM, 888°M, 88e 88 [‌88‌]
MeMM, MMM, eeeeee, 88e 88 [‌88‌]
MeMM, MMM, 888°M, 8e 88 [‌88‌]
MeMM, MMM, 888°M, 8e 88 [‌88‌]
MeMM, MMM, 888°M, 8e 88 [‌88‌]

Meeeeeeeeeeeee eeeeeeee, eeeeeeeee eeee 8,8-eeeeeeeeeeeeeee ee eeeeeeee eeee eeeeee(M) eeeeeee, eee eeeeee eeeeeeeeeee ee e eeeee eeeeee ee eee eeeeeeeeeeeee eeeeee eeeeeeeeeeeeeee. Meeeee eeeeeeeeeeeeeee eee eeeeeeeee ee eeee eeeeee eeeeeee eeeeeeee eee eee eeeeee eeeeeee eeeee eee eeeeeeeeeeeeeee eee eeeeeeeee eeee e eeeeeeee eeeeeee. Me eeee eeeee, eeeeeee eeeeeeeeeeeeeee eeee eeeeee(M) eeeeeee eeee eeee eeeeeeee ee eeeeee eeeeeeeeeeeeeee, ee ee eee eeee eee eeeee eeeee eeeeeeeeee.[‌88‌] Meee ee eeee eee eeeeee ee eeeeeeeeeee ee ee eeeeeeeee eeeeee eeeee eeeee eeeeeeeeeeeeee; eeeeeee, eee eeeee ee eeee 88%.[‌88‌]

Me eeeeee, eeeeeeeeeee ee eeeeeee ee eeee eeeeeee eeee eee eeeee eeeee eeeee eeeeee(M) eeeeeee ee eee eeeeeeee eeeeeeeee ee eeeeeeeee eeee eeeeeeee, eeeeeeeeee eee eee eeeeeeeeeeeeeee eeee ee eee eeeeeeeee ee eeeee eeeeeeeeeeeeeee. Meeeeee, eee eeeeeeee ee eeeeeeeeee eee eeeeeee ee eee eeeeeeee eeeeeeeeee, eeeeeeeee eeeeeee, eeeeeeeeeee, eeee, eeeeeeeeee ee eee eeeeeeee eeeeeeee eee eeeeeee, eee eee eeeeeeee eeeeeee. Meeeeeeeee eeeeee eeee eeee eeeeeeee ee eeeeeee eeeee eeeeeeeeee eeeeeeeeeee. Meeee eee eeeeeeeeeeeee eeeeeeeee ee eeee eeeeeee, eee eee ee eeeeeeeeeeeeeeeee ee eeeeeee eee e eeeeeeeeeee ee 888°M ee e eeeeeee eeeeee eee eee eeeeeeeeeee ee eeee eeeeeeee eeee eeee eeeeeee ee eeeeeeeeeee ee ee eeeee ee eee eeeee eeeeeeee.

Meeeeeeeeeee Meeeeeeee

8,8-Meeeeeeeeeeeeeeeeeeeeeeeee (88):[‌88‌]

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

M eeeeeeeeee ee 8,8-eeeeeee-8,8-eeeeeeeeeeeeeeee (88; 88e, 8.88eee) eee MeMM (88.8e, 8.88eee) ee MMM (888eM) eee eeeeeee ee 888°M (eee eeee) eee 88e. Mee eeeeeee eee eeeeeee ee eeee eeeee eeeeeeee eee eeeeee eeee M8M (888eM). Meeee eeeeeeee eee 8e, eee eeeeeee eee eeeeeeee eee eee eeeee eeeeeee eee eeeeeee eeee e eeeeeee ee eeeeeeeeeeeeeee/M8M (8:8) eee 8e eee eeeeeeee. Meee eeeeeeeee eee eeeeeeee eeeee eee eeeeeeee eee eeeeeeeee. Mee eeeeeeee eeee eee eeeeee eeee M8M eee eeeee ee eeeee ee eeeeee eee eeeee eeeeeeee; eeeee: 88.88e (88%).

8,8-Meeeee-8-ee-8-ee-8,8-eeeeeeeeeeeeeeeeeeeee (88):[‌88‌]

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

M eeeeeee ee 8,8-eeeeeee-8,8-eeeeee-8-ee-8-ee-8,8-eeeeeeeeeeeeeee (88; 8.8e, 88eeee) eee MeMM (8.8e, 88eeee) eee eeeeeeee ee MMM (88eM) eeeee M8 eee 88e. Meeee eeeeeee, eee eeeeeee eee eeeeee eeee eeeee ee MM8 (888eM) eee e eeeeee eeeeee ee eee eee eeeeeee eeeeeee eee eeee eee 8e. Mee eeeee eeeeeee eee eeeeeee eeeeeeee, eeeeee eeee M8M (888eM), eee eeeee (Me8MM8). Me eee eeee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, eeeeeee, Me 8.8) ee eeee eee eeeee eeeeeeee ee ee eee-eeeee eeeee; eeeee: 8.8e (88%); ee 88°M.

References