Nitric Acid → HCID 19827845, compound

Participants

Reaction Steps

A solution of 100% nitric acid (0.91 ml, 22 mmol) in 8 ml of acetic anhydride was added dropwise to a solution of 1-cyano-4-methoxynaphthalene (3.66 g, 20 mmol) in 50 ml of acetic anhydride containing two drops of conc. sulfuric acid while maintaining the temperature at -30° to -40° C. The mixture was stirred for an additional 10 min. and filtered. The solid was washed with water and dried to give 3.5 g (77%) of 4-cyano-1-methoxy-2-nitronaphthalene. The crude product was dissolved in a mixture of 25 ml of tetrahydrofuran and 10 ml of N,N-dimethylformamide. Then 5 ml of cyclohexylamine was added, and the mixture was stirred at room temperature for 2 h. The mixture was evaporated to dryness, and the residue was triturated with light petroleum to give 4,5 g (90%) of 4-cyano-1-cyclohexylamino-2-nitronaphthalene. The crude product, suspended in 200 ml of 96% ethanol was hydrogenated at room temperature and atmospheric pressure in the presence of 5% palladium-on-carbon. When the theoretical amount of hydrogen was taken up, the catalyst was filtered off, and the filtrate was evaporated to dryness. The resulting diaminonaphthalene was immediately suspended in a mixture of 20 ml of dry tetrahydrofuran and dry triethylamine (1.95 ml, 14 mmol). Then a solution of ethyl oxalylchloride (1.56 ml, 14 mmol) in 10 ml of dry tetrahydrofuran was added dropwise with stirring at 0° C. The mixture was stirred at room temperature over night, and then heated at reflux for 1 h. The cooled mixture was filtered, and the solid was washed with tetrahydrofuran and water. Recrystallization from 2-methoxyethanol afforded 1.84 g (41%) of the title compound. M.p. >300° C.; IR (KBr): 2220, 1700 cm-1 ; 1 -NMR (DMSO-d6): 0.93-4.77 (m, 11H, cyclohexyl), 7.97-8.63 (m, 5H, ArH), 11.8 (broad s, 1H, NH); MS (m/z): 319 (M+, 16%).

Provenance & Evidence