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12.3.1.4.3.4 Method 4: Syntheses Based on the Use of Diaminomaleonitrile

DOI: 10.1055/sos-SD-012-00398

Grimmett, M. R.Science of Synthesis, (200212378.

Diaminomaleonitrile (DAMN, 108) is a highly versatile reagent for imidazole synthesis. It can be converted by reaction with a nitrilium triflate into an amidine salt that can be cyclized to form an imidazol-2-amine, it reacts directly with formimidamide, with ortho esters, and, in the form of its imidate, it cyclizes with ammonia or a primary amine. All of these reactions involve formation of the imidazole 15 bond (Section 12.3.1.6.2). Oxidative cyclization of the Schiff bases formed when diaminomaleonitrile (108) reacts with carbonyl reagents is described as a 12 bond formation (Section 12.3.1.6.1.7).

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Meeeee 88 Meeeeeee ee Meeeeeeeeeeeeeeeeee Me Meee 8-Meeee-8M-eeeeeeeee-8-eeeeeeeeeee[‌888‌,‌888‌]

Meee 8,8-eeeeeeeeeeeeeeeeeeeee eeeeee eeee eeeeeeeeeeeeeee eeeeeeeee, eee 8M-eeeeeeeee eeeeeeee eeeeeeeee eeeeeeeee ee eeeeeeeeee eee eeeeeeeeeeee ee 8,8-eeeeeee-8M-eeeeeeeee-8,8-eeeeeeeeeeeeeee.[‌888‌,‌888‌,‌888‌]

Meeeeeeeeeee Meeeeeeeee

8-(eeee-Meeeeeeeee)-8M-eeeeeeeee-8,8-eeeeeeeeeeeeee (888):[‌888‌]

Me e eeee ee eeee-eeeee eeeeeeeeee (8.8e, 88eeee) ee MMM (888eM) eee eeeee MMMM (888; 8.8e, 88eeee). Mee eeeeeeeeeee eeee ee eeeee 88°M, eee e eeeeeeeeeee eeeeee. Meeee eeeeeeee eee 88e eee eeeeeeeeeee eee eeeeeeeeee eeeeeeeeeee, eee eee eeeeeeeee eeee eeee eee eeeeeeeeeeeeeee (eeeeee eee, MMMe8) ee eeee eee eeeeeee; eeeee: 8.88e (88%). Meeeeeeeeeeeeeeee (Me8M/eeeeeeeee eeeee) eeee eee eeeeeee ee eeeee eeeeeee; ee 888888°M.

8-(Meeeeeeeee)-8M-eeeeeeeee-8,8-eeeeeeeeeeeeee (888, M8=Me):[‌888‌]

Me e eeeeeeeeee ee MMMM (888; 8.8e, 88eeee) ee eee eeeeeee (888eM) e eeee ee M-(eeeeeeeeeeeeeeeee)eeeeeeeeeeeeeeeeee (8.8e, 88eeee) ee eeeeeee (888eM) eee eeeee eeeeeeee eeee eeeeeeee eeeeeeee. Mee eeeeeee eee eeee eeeeeeee eee 888e, eeeeee, eee eee eeeeeeeeeee eeeeeeee eee eeeeeeeeeeeeee (MeMM); eeeee: 8.88e (88%); ee 888888°M. Meeeeeeee eeeeeeee eeee eee eeeeeeeee:

8-[(Meeeeeeeeeeeee)eeeee]-8M-eeeeeeeee-8,8-eeeeeeeeeeeeee (888, M8=Me); eeeee: 88%.

8-(Meeeeeeeee)-8M-eeeeeeeee-8,8-eeeeeeeeeeeeee (888, M8=8-Mee); eeeee: 88%.

8-{[(8-Meeeeeeeeeee)eeeeeeee]eeeee}-8M-eeeeeeeee-8,8-eeeeeeeeeeeeee (888, M8=8-MeM8M8); eeeee: 88%.

8-{[(8-Meeeeeeeeeeee)eeeeeeee]eeeee}-8M-eeeeeeeee-8,8-eeeeeeeeeeeeee (888, M8=8-MeMM8M8); eeeee: 88%.

8-{[(8-Meeeeeeeeee)eeeeeeee]eeeee}-8M-eeeeeeeee-8,8-eeeeeeeeeeeeee (888, M8=8-M8MM8M8); eeeee: 88%.

8-Meeee-8M-eeeeeeeee-8-eeeeeeeeeee (888):[‌888‌]

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References