Stannous chloride dihydrate → 4-Bromo-6-(1,1,1-trifluoro-2-methylpropan-2-yl)pyridin-3-amine

HRID 1050161Notes

Reaction equation

[Br:1][C:2]1[C:7]([N+:8]([O-])=O)=[CH:6][N:5]=[C:4]([C:11]([CH3:17])([CH3:16])[C:12]([F:15])([F:14])[F:13])[CH:3]=1.O.O.[Sn](Cl)Cl.C([O-])(O)=O.[Na+]>CCO>[Br:1][C:2]1[CH:3]=[C:4]([C:11]([CH3:16])([CH3:17])[C:12]([F:13])([F:14])[F:15])[N:5]=[CH:6][C:7]=1[NH2:8]

Participants

Conditions

Temperature: 85 °C

Procedure

To a mixture of 4-bromo-5-nitro-2-(1,1,1-trifluoro-2-methylpropan-2-yl)pyridine (50 mg, 0.160 mmol) in EtOH (10 mL) was added tin(II) chloride dihydrate (180 mg, 0.799 mmol). The mixture was stirred at 85° C. for 16 h. Then the mixture was added to an aqueous NaHCO3 solution. The mixture was extracted with EA (50 mL×2). The combined organic extracts were washed with brine, dried over MgSO4, filtered and concentrated. The crude material was purified by preparative TLC (PE/EA=2:1, Rf=0.5) to yield a light yellow solid of 4-bromo-6-(1,1,1-trifluoro-2-methylpropan-2-yl)pyridin-3-amine (30 mg, 0.090 mmol, 56.4% yield): 1H NMR (400 MHz, CD3OD): δ 8.05 (s, 1H), 7.58 (s, 1H), 1.56 (s, 6H). ES-LCMS m/z 283.1 (M+H).

Workup

extractionThe mixture was extracted with EA (50 mL×2)
washThe combined organic extracts were washed with brine
dry with materialdried over MgSO4
filtrationfiltered
concentrationconcentrated
customThe crude material was purified by preparative TLC (PE/EA=2:1, Rf=0.5)

Sources & evidence

ORD record: ord-aa4db6e3e9a843df9ac5cada2c6a0551
Source dataset: uspto-grants-2016_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09382238B2

Reaction notes

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