Stannous chloride dihydrate → N4-(4-methoxybenzyl)-6-bromopyridine-3,4-diamine

HRID 40668Notes

Reaction equation

O.O.[Sn](Cl)Cl.[CH3:6][O:7][C:8]1[CH:25]=[CH:24][C:11]([CH2:12][NH:13][C:14]2[C:19]([N+:20]([O-])=O)=[CH:18][N:17]=[C:16]([Br:23])[CH:15]=2)=[CH:10][CH:9]=1>CCO>[CH3:6][O:7][C:8]1[CH:9]=[CH:10][C:11]([CH2:12][NH:13][C:14]2[CH:15]=[C:16]([Br:23])[N:17]=[CH:18][C:19]=2[NH2:20])=[CH:24][CH:25]=1

Participants

Conditions

Temperature: 70 °C

Procedure

Tin (II) chloride dihydrate (4.37 g, 19.4 mmol) was added portionwise to N-(4-methoxybenzyl)-2-bromo-5-nitropyridin-4-amine (1.31 g, 3.87 mmol) in absolute EtOH (10 mL) at room temperature. The mixture was then heated at 70° C. for 2 hours before being concentrated in vacuo. The residue was suspended in a mixture of ethyl acetate and saturated sodium bicarbonate solution and filtered. The insoluble solids were washed with EtOAc. The aqueous phase was re-extracted with ethyl acetate and the combined organic layers were washed with brine, dried (Na2SO4) and concentrated to give the title compound as a brown solid (1.05 g, 3.41 mmol, 88%). 1H NMR (d6-DMSO, 400 MHz) δ 7.40 (s, 1H), 7.30 (d, 2H, 8.6 Hz), 6.90 (d, 2H, 8.6 Hz), 6.45 (s, 1H), 6.3 (br t, 1H, 5.5 Hz), 4.85 (br s, 2H), 4.3 (d, 2H, 5.5 Hz), 3.75 (s, 3H). LCMS (1) Rt=1.77 min; m/z (ESI−) 306, 308; (ESI+) 308, 310.

Workup

concentrationbefore being concentrated in vacuo
additionThe residue was suspended in a mixture of ethyl acetate and saturated sodium bicarbonate solution
filtrationfiltered
washThe insoluble solids were washed with EtOAc
extractionThe aqueous phase was re-extracted with ethyl acetate
washthe combined organic layers were washed with brine
dry with materialdried (Na2SO4)
concentrationconcentrated

Sources & evidence

ORD record: ord-89a29208978d4ad1a232ce7dbce26b84
Source dataset: uspto-grants-2013_09
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08530468B2

Reaction notes

Loading…