Phosphorus oxybromide → 4-Bromo-5-nitro-2-(1,1,1-trifluoro-2-methylpropan-2-yl)pyridine

HRID 1050160Notes

Reaction equation

[N+:1]([C:4]1[C:5](=O)[CH:6]=[C:7]([C:10]([CH3:16])([CH3:15])[C:11]([F:14])([F:13])[F:12])[NH:8][CH:9]=1)([O-:3])=[O:2].P(Br)(Br)([Br:20])=O.C([O-])(O)=O.[Na+]>ClCCCl>[Br:20][C:5]1[C:4]([N+:1]([O-:3])=[O:2])=[CH:9][N:8]=[C:7]([C:10]([CH3:16])([CH3:15])[C:11]([F:14])([F:13])[F:12])[CH:6]=1

Participants

Conditions

Temperature: 85 °C

Procedure

To a mixture of 5-nitro-2-(1,1,1-trifluoro-2-methylpropan-2-yl)pyridin-4(1H)-one (100 mg, 0.400 mmol) in DCE (10 mL) was added phosphoryl tribromide (138 mg, 0.480 mmol). The mixture was stirred at 85° C. for 1 h. Then the mixture was added to 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 to afford 4-bromo-5-nitro-2-(1,1,1-trifluoro-2-methylpropan-2-yl)pyridine (60 mg, 0.096 mmol, 24.0% yield). TLC (PE/EA=10:1, Rf=0.6): 1H NMR (400 MHz, CD3OD): δ 8.74 (s, 1H), 6.83 (s, 1H), 1.54 (s, 6H). ES-LCMS m/z 312.9 (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

Sources & evidence

ORD record: ord-6f655889f98f48e29bfc84a5383ec90f
Source dataset: uspto-grants-2016_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09382238B2

Reaction notes

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