Nucleophilic Aromatic Substitution Reactions on 4, 5-Dicyano-2-fluoro-1-methylimidazole: Syntheses and Properties of 4, 5-Dicyano-1, 3-dimethyl-2-imidazolone and its Pseudooxocarbon Derivatives

Article type: Research Article

Authors: Subrayan, Ramachandran P. | Rasmussen, Paul G.

Affiliations: Department of Chemistry, The University of Michigan, Ann Arbor, MI 48109-1055, U.S.A

Note: [] Present address: Coatings Research Institute, Eastern Michigan University, Ypsilanti, MI 48197

Note: [] Corresponding author.

Abstract: Nucleophilic aromatic substitution (SN Ar) reactions of 4, 5-dicyano-2-fluoro-1-methylimidazole using disodium cyanamide or disodium malononitrile followed by methylation using dimethyl sulfate gave the 2-cyanimino and 2-dicyanomethylene pseudooxocarbon derivatives 4 and 6. The oxocarbon analog of 4 and 6, namely 4, 5- dicyano-1, 3-dimethyl-2-imidazolone (7), was synthesized by dimethylation of 4, 5- dicyano-2-imidazolone which, in turn was synthesized from diaminomaleonitrile (DAMN) and triphosgene. These compounds belong to the class of oxo and pseudooxocarbon compounds. Thermogravimetric analysis of 6 shows a 30 wt.% loss which might suggest the loss of the dicyanomethylene group. The fluorescence spectra of these compounds show strong emissions in the order, 6 (475 nm) < 4 (400 nm) < 7 (345 nm). Cyclic voltammetry of these compounds in CH3CN shows irreversible cyclic voltammograms around – 2.0 volts vs. Ag/Ag+. Compound 6 forms long crystals of weak, red-colored charge transfer complexes with tetrathiafulvalene.

DOI: 10.1080/13583149712331338879

Journal: Main Group Chemistry, vol. 2, no. 1, pp. 51-60, 1997