2,6-Dichloro-3-nitropyridin-4-amine → 6-Chloro-2-methyl-3-nitropyridin-4-amine

Temperature

70 °C

To a pressure vessel, a degassed solution of 2,6-dichloro-3-nitro-pyridin-4-ylamine (3.0 g, 14.4 mmol) (R. J. Rousseau and R. K. Robins J. Heterocyclic Chem. 2, 1965, 196) and tetrakis(triphenylphosphine)palladium(0) (1.67 g, 1.44 mmol) in DMF (45 mL) was stirred at room temperature. To this mixture was added dropwise a solution of trimethylaluminium (7.93 mL, 15.8 mmol, 2M in toluene). The resulting mixture was sealed and heated at 70° C. for 3 hours. The reaction mixture was poured into ice/water (800 mL). The organic material was extracted with EtOAc (5×200 mL). The combined organic layers were dried (MgSO4) and concentrated in vacuo. The crude material was purified on silica gel dry column using EtOAc:Hexane gradient (1:9) to (3:7) to afford the desired compound as a yellow solid (1.20 g, 45%), HPLC: 99% (220 nm), LCMS (+ESI, M+H+) m/z 188, IR (KBr, cm−1) 3431, 3310, 3172, 1653, 1506, 1264; 1H NMR (400 MHz, CDCl3) δ 7.19 (s, 1H), 6.57 (br s, 2H), 2.63 (s, 3H);.

1. customThe resulting mixture was sealed
2. extractionThe organic material was extracted with EtOAc (5×200 mL)
3. dry with materialThe combined organic layers were dried (MgSO4)
4. concentrationconcentrated in vacuo
5. customThe crude material was purified on silica gel
6. customdry column

ORD record

ord-82338118339043deb75217f7a4411ca1

Source dataset

uspto-grants-2008_12

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US07470696B2