Synthesis, Characterization, and Thermolysis of C(15)N(12)

Eric C. Coad; Jeff Kampf; Paul G. Rasmussen

doi:10.1021/jo960828x

Synthesis, Characterization, and Thermolysis of C(15)N(12)

J Org Chem. 1996 Sep 20;61(19):6666-6672. doi: 10.1021/jo960828x.

Authors

Eric C. Coad¹, Jeff Kampf, Paul G. Rasmussen

Affiliation

¹ The Willard H. Dow Laboratories, Department of Chemistry, The University of Michigan, Ann Arbor, Michigan 48109-1055.

PMID: 11667538
DOI: 10.1021/jo960828x

Abstract

Synthesis of 1-methyl-2-fluoro-4,5-dicyanoimidazole was done by halogen exchange between 1-methyl-2-bromo-4,5-dicyanoimidazole and potassium fluoride. Halogen exchange between 1-methyl-2-bromo-4,5-dicyanoimidazole and lithium chloride in N-methylpyrrolidinone at 150 degrees C yielded 1-methyl-2-chloro-4,5-dicyanoimidazole, and additional heating to 210 degrees C resulted in the demethylation to yield 2-chloro-4,5-dicyanoimidazole. Thermolyses of the 2-halo-4,5-dicyanoimidazole derivatives (F, Cl) and 1-iodo-2-halo-4,5-dicyanoimidazole derivatives (Cl, Br, I) between 100 and 290 degrees C were found to yield Tris(imidazo)[1,2-a:1,2-c:1,2-e]-1,3,5-triazine-2,3,5,6,8,9-hexacarbonitrile, or HTT, with (C(5)N(4))(3) composition. HTT has been characterized and purified and the crystal structure obtained. Thermolysis of HTT at 490-500 degrees C gives a material with C/N = 1.020. The thermal properties of HTT and its decomposition products show thermal stability to 350 degrees C.