Science of Synthesis

Grimmett, M. R., Science of Synthesis, (2002) 12, 378.

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 1—5 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 1—2 bond formation (Section ‌12.3.1.6.1.7‌).

Meee eeeeeeeeeeeeeeeeeee (‌888‌) (ee eee ee eee eeeeeeeeeee) ee eeeeee eeee ee eeeee eeeee ee eeeeeee eeeeeeee, eeeeeeeee-8,8-eeeeeeeeeeeeeee eee eeeeee,[‌888‌,‌888‌] e.e. eeeeeeeee ee 8M-eeeeeeeee-8,8-eeeeeeeeeeeeee (‌888‌) (‌Meeee 8‌).[‌888‌] Meee eeeee ee eeeeee eeeee eeeee eeeeeee eee 8-eeeeeeeeeeeeee-8,8-eeeeeeeeeeeeee eeeeeee. (Mee eeee Meeeeee ‌88.8.8.8.8‌; 8—8 eeee eeeeeeeee.) Meeeee eeee ee eeeeeeeee eeeeee eeeeeeee eeeeeeeeeeeeeeeeeee (‌888‌) eeee 8-eeeee-8M-eeeeeeeee-8-eeeeeeeeeee (‌888‌) (‌Meeeee 88‌).[‌888‌,‌888‌] Meeeeeee eeeeeeee ee eeeee eeeeeeeeeeee eeeeeeeeeee eeeeeee ‌888‌ eeee 8-eeeee-8M-eeeeeeeee-8,8-eeeeeeeeeeeeee (‌888‌) ee, eee eeeeeee, 8-(eeee-eeeeeeeeee)-8M-eeeeeeeee-8,8-eeeeeeeeeeeeee (‌888‌), eeeeeeeeeeee.[‌888‌,‌888‌] Meeeeeee eeee eeeeeeee eeeee 8-eee-8,8-eeeeeee-8M-eeeeeeeee-8,8-eeeeeeeeeeeeee (‌888‌),[‌888‌,‌888‌] eee eeee M-(eeeeeeeeeeeeeeeee)eeeeeeeeeeee 88–88% eeeeee ee 8-eeeeeeeeeeeee eeeeeeeeeee ‌888‌ eee eeeeee; eee eeeeeee, 8-(eeeeeeeeee)- eee 8-[(eeeeeeeeeeeeee)eeeee]-8M-eeeeeeeee-8,8-eeeeeeeeeeeeee (‌888‌, M8 = Me eee Me) eee eeeeee ee 88 eee 88% eeeee, eeeeeeeeeeee.[‌888‌] Meeeeee eeeeeeeeeeeeee eeee ‌888‌ eeee 8-eeeeeeeeeeeeee-8,8-eeeeeeeeeeeeeee, e.e. eeeee eeeeeeeeeee eeeee 8-eeeeee-8M-eeeeeeeee-8,8-eeeeeeeeeeeeee (‌888‌).[‌888‌] ‌Meeee 8‌ eeeeeeeeee eeeee eeeeeeeee. Meee eeeeee eeee ee eee eeeeeeeee eeeeeee, eee eeeeeeee eeeeeeeeee eeeeeee eee eeeeeee. Me eee eeeeeee ee eeeeee eeeeee eeeee eeeeee ee eee eeeeeee eee 88 eeeeeee, eee ee eee eeeee eeeeee ee ‌888‌ ee eeeeeeeeee; eeeeeeeee eee eee eeeee ee eeeeeee eeeee ee eee eeeeeeeee ee 8M-eeeeeeeee-8,8-eeeeeeeeeeeeee (‌888‌); ee eeeeeeeee eeeeee eee ee eee eeeee eeeeee ee eeeeeeee ee eeee ‌888‌.[‌888‌,‌888‌]

‌Meeee 8‌ Meeeeeeee ee Meeeeeeeeeeeeeeeeee Me Meee Meeeeeeee-8,8-eeeeeeeeeeeeeee[‌888‌–‌888‌,‌888‌,‌888‌]

Meeeeee, Meeeeeeeee	Meeeeee	Meeeee	Meeee (%)	Mee
MM(MMe)8, eeeeeee, 888°M MMM8M, eeeeeee, eeee		‌888‌	88 88	[‌888‌] [‌888‌]
MeMM, MMM, 8–88°M MMM, MMMe8, 888°M		‌888‌	88 88	[‌888‌,‌888‌] [‌888‌]
Me8M=Me-Me, MMM, ee, 88 e		‌888‌	88	[‌888‌]
MMMe8, MeMM, eeeeeee, 88°M		‌888‌	88	[‌888‌]
Me8M=MMM8M8, eeeeeee, eeee		‌888‌	M8 = Me 88 M8 = Me 88	[‌888‌]
MeM(MM)MMe, eeeeeee, eeee, 8 e		‌888‌	88	[‌888‌]

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

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

Me e eeeeeeeeee ee MMMM (‌888‌; 8.8 e, 88 eeee) ee eee eeeeeee (888 eM) e eeee ee M-(eeeeeeeeeeeeeeeee)eeeeeeeeeeeeeeeeee (8.8 e, 88 eeee) ee eeeeeee (888 eM) eee eeeee eeeeeeee eeee eeeeeeee eeeeeeee. Mee eeeeeee eee eeee eeeeeeee eee 8–88 e, eeeeee, eee eee eeeeeeeeeee eeeeeeee eee eeeeeeeeeeeeee (MeMM); eeeee: 8.88 e (88%); ee 888–888°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]

M eeeeeee ee MMMM (‌888‌; 8 e, 88 eeee), MMM8M (8 eM, 888 eeee), eee eeeeee (888 eM) eee eeeeeee ee ee eee 88 eee, eeee eeeeee eeeee eeeeee eee 8 e. Mee eeee eeeee eeee eeeeee eee eeeeeeeee, eeeeee eeee Me8M, eee eeeeeeeee eeeeeeeeee eeee eee M8M. Meeeeeeeeeeee ee eee eeeeeee eeeeeeee eeee eee eeeeeee; eeeee: 8.8 e (88%); ee 888°M. Meee eee eeeeeee eee eeeeeeee 8M-eeeeeeeee-8,8-eeeeeeeeeeeee; eeeee: 8.88 e (8%); ee >888°M.

References

Meeeeee Meeeeeeeeee

• 8.Meeeee-Meee, (8888) 8/8e, 88.
• 8.Meeeee-Meee, (8888) M 8e, 88.
• 8.Meeeee-Meee, (8888) M 8e8, 888.