3,4-Diaminopyridine → Pyrido[3,4-b]pyrazine

Temperature

70 °C

2.00 g (18.33 mmol) of 3,4-diaminopyridine were added to a solution of 2.82 ml of glyoxal (40 wt. % in water, ρ=1.265 g/ml, 62.48 mmol) in 30 ml of ethanol. The reaction mixture was maintained at an oil bath temperature of 70° C. for 5 hours and after cooling to room temperature the solvent was distilled off on a rotary evaporator. The crude product was purified by flash chromatography (EtOAc/isohexane, 9:1). This gave 2.35 g (17.96 mmol, 98%) of a white powder. Rf=0.27 (isohexane/EtOAc, 1:9). 1H NMR (200 MHz, CDCl3): δ=7.94 (dd, 3J=5.8 Hz, 4J=0.6 Hz, 1H, H-7), 8.83 (d, 3J=5.8 Hz, 1H, H-8), 8.96 (d, 3J=1.6 Hz, 1H, H-3), 9.02 (d, 3J=1.6 Hz, 1H, H-2), 9.56 (d, 4J=0.6 Hz, 1H, H-5) ppm. 13C NMR (100 MHz, CDCl3): δ=121.6 (CH, C-7), 138.0 (Cq), 145.3 (Cq), 147.3 (C—H, C-8), 146.5 (C—H, C-3), 149.2 (CH, C-2), 154.8 (C—H, C-5) ppm. GC-MS (EI): RT 5.45 min, m/e (%): 132 (8), 131 (M+, 100), 104 (25), 77 (13), 50 (10) IR (KBr): ν=3435 (vs), 3092 (w), 3023 (m), 1969 (w), 1758 (w), 1631 (w), 1598 (vs), 1562 (m), 1536 (w), 1488 (s), 1436 (vs), 1416 (m), 1381 (m), 1351 (w), 1290 (w), 1279 (m), 1212 (m), 1201 (m), 1148 (w), 1033 (s), 1014 (s), 972 (w), 959 (vs), 931 (m), 881 (vs), 838 (m), 824 (s), 773 (w), 651 (s), 623 (m), 546 (w), 524 (w), 457 (s) cm1.

1. temperatureafter cooling to room temperature the solvent
2. distillationwas distilled off on a rotary evaporator
3. customThe crude product was purified by flash chromatography (EtOAc/isohexane, 9:1)
4. customRT 5.45 min, m/e (%)

ORD record

ord-8f7eb209b84e4cb1bbc62044db6497f8

Source dataset

uspto-grants-2011_08

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US07994169B2