Science of Synthesis

Subramanian, L. R., Science of Synthesis, (2004) 19, 182.

Both 13C- and 14C-labeled aryl cyanides are of interest because they can be converted into versatile labeled synthetic intermediates such as carboxylic acids, primary amides, benzylamines, and aldehydes. To avoid having to prepare the labeled copper(I) cyanide, readily available labeled potassium cyanide is used as the cyano transfer reagent for aryl iodides to afford labeled aryl cyanides.[‌47‌] This works well in the presence of 0.5 equivalents of copper(I) iodide in refluxing 1-methylpyrrolidin-2-one, e.g. the preparation of 9-benzyl-7-fluoro-9H-carbazole-2-(1-13C)-carbonitrile (‌31‌) from the iodide ‌30‌ (‌Scheme 12‌).[‌47‌] Dimethylformamide and dimethylacetamide have also been used as solvents in certain cases. Fluorine substituents are not affected, and in one example the iodo group is selectively cyanated even when a bromo substituent is present. Otherwise, in compounds with mixed halogen substituents, each halide is replaced by cyano groups in differing proportions.

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‌Meeeee 88‌ Meeeee-Meeeeeeee Meeeee Meeeee Meeeeeee–Meeeeeeee ee ee Meee Meeeeee[‌88‌]

Meeeeeeeeeee Meeeeeeee

8-Meeeee-8-eeeeee-8M-eeeeeeeee-8-(8-88M)-eeeeeeeeeeee (‌88‌); Meeeeee Meeeeeeee:[‌88‌]

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

M eeeeeee eeeeeee ee 8-eeeeee-8-eeeeee-8-eeee-8M-eeeeeeeee (‌88‌; 8.88 e, 8.88 eeee), M88MM (888 ee, 8.88 eeee), eee eeeeee eeeeee MeM (888 ee, 8.88 eeee) ee MMM (8 eM) eee eeeeeeee eeeee M8 eee 8 e. Mee eeee eeeeeee eee eeeeeee ee eeee ee 88°M, eee eeeeeee eeee MeMMe (888 eM). Mee eeee eee eeeeeeeee eeeeeeeeeeee eeee 8% ee MeMe8 (e/e, 888 eM), M8M (888 eM), MeMMM8 ee M8M (8.8 e ee 888 eM), M8M (888 eM), eee eeeee (888 eM), eee eee eeee eeeee (MeMM8). Mee eeeeeee eee eeeeeee ee eeeeeeeeeee, eee eee eeeeeee eee eeeeeeee ee eeeeeeeeeeeeee (888 e eeeeee eee, MM8Me8/MeMMe 8:8). Mee eeeee eeeeeeeeeee eeeeeee eee eeeee eee 88 e ee 88°M ee eeeee ee eeee eee eeeeeee; eeeee: 8.888 e (88% eeee M88MM). Mee eeeeeee eeeee ee eeeeeeeeeeeeee (eeeeeeeeeee).

8,8-Meeeeeeeeeeeeeeeeeeee (‌88‌); Meeeeee Meeeeeeee:[‌88‌]

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

M Meeeeee eeee eee eeeeeee eeee MeMM (888 ee, 8.88 eeee), 88 eee% MeM (88 ee, 8.88 eeee), eee 88 eee% MM (888 ee, 8.888 eeee), eee eee eeeeeee eeeeeeeee eee eeeeeeeeee eeee eeeee (8 ×). Mee eeeeeee (8.8 eM), M,M′-eeeeeeeeeeeeee-8,8-eeeeeee (888 μM, 8.88 eeee), eee 8-eeeee-8,8-eeeeeeeeeeeeeeee (‌88‌; 888 μM, 8.88 eeee) eeee eeeee eeeee eeeee. Mee Meeeeee eeee eee eeeeee eeee e Meeeee eeeee eee eee eeeeeee eee eeeeeee ee 888°M eee 88 e. Mee eeeeeeeee eeeeeeeeee eee eeeeeee ee eeeee ee, eeeeeee eeee 88% ee MM8 (8 eM), eee eeeeeeeee eeee MeMMe (8 × 8 eM). Mee eeeeeeee eeeeeee eeeeee eeee eeeee (MeMM8) eee eeeeeeeeeeee, eee eee eeeeeee eee eeeeeeee ee eeeeeeeeeeee ee eeeeeee eeeeeeee (888°M/8 Meee) ee eeeeeee e eeeeee eeeee; eeeee: 888 ee (88%); ee 88–88°M.

References

Meeeeee Meeeeeeeeee

• 8.Meeeee-Meee, (8888) 8/8e, 888.
• 8.Meeeee-Meee, (8888) M 8-8, 8888.