Nitric Acid → 5-[(4-Methyl-8-nitroquinolin-6-yl)methyl]pyrimidine-2,4-diamine

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Reaction Steps

The product of Example 11 (0.53 g, 2 mmol) was dissolved in 7 ml of concentrated sulfuric acid, and chilled to 0°. Then 0.3 ml (6.4 mmol) of fuming nitric acid (d=1.5) in 0.5 ml of concentrated sulfuric acid was added dropwise to the solution. The reaction was stirred at 0°-5° for 30 minutes, then at 25° for 1 hour. It was then poured onto 50 ml of ice and neutralised to pH 9 with concentrated ammonium hydroxide. The precipitate which formed was filtered and dried, and then purified on a silica gel column which was eluted with methylene chloride:methanol/12:1, giving 0.33 g (53%) of the title compound, which melted at 256°-258° after recrystallisation from beta methoxyethanol:water/2:1. NMR (Me2SO-d6) δ 2.72 (s, 3, Me), 3.90 (s, 2, CH2), 5.77 (br s, 2, NH2), 6.24 (br s, 2, NH2), 7.55 (d, 1, pyridine-beta H, J=4.1), 7.71 (s, 1, pyrimidine-H6), 8.05 (d, 1, ArH5, J=1.8), 8.28 (d, 1, ArH7, J=1.6), 8.81 (d, 1, pyridine-alpha H, J=4.4). Anal. Calcd. for C15H14N6O2 0.5H2O: C, 56.42; H, 4.73; N, 26.32. Found: C, 56.34; H, 4.82; N, 26.21.

Provenance & Evidence