Dimethyl Sulfate → 6-Bromo-3-methoxy-2-nitropyridine

HRID 1770821Notes

Reaction equation

HRID 1770821 reaction equation
[Br:1][C:2]1[N:7]=[C:6]([N+:8]([O-:10])=[O:9])[C:5]([OH:11])=[CH:4][CH:3]=1.Br[C:13]1C=C(Br)N=C([N+]([O-])=O)C=1O.C([O-])([O-])=O.[K+].[K+].S(OC)(OC)(=O)=O>CN(C)C=O>[Br:1][C:2]1[N:7]=[C:6]([N+:8]([O-:10])=[O:9])[C:5]([O:11][CH3:13])=[CH:4][CH:3]=1

Participants

6

Reactant 4

HCID 6497Dimethyl SulfateHCID 11430Potassium CarbonateHCID 218738086-Bromo-2-nitropyridin-3-olHCID 575629084,6-Dibromo-2-nitropyridin-3-ol

Product 1

HCID 226151626-Bromo-3-methoxy-2-nitropyridine

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
60 °C

Procedure

To a heterogeneous 60:40 mixture of 6-bromo-3-hydroxy-2-nitropyridine (30): 4,6-dibromo-3-hydroxy-2-nitropyridine (31) (2.18 g, 10 mmol), K2CO3 (2.08 g, 15 mmol) in N,N-dimethylformamide (DMF) (20 mL) was added dimethyl sulfate (DMS) (1.13 mL, 12 mmol) and the resulting mixture was stirred at 60° C. for 24 hours. The reaction mixture was poured over ice-water (100 mL), extracted with ethyl acetate (3×50 mL), and the organic phase was dried over anhydrous sodium sulfate. The solvent was then removed under reduced pressure to afford 6-bromo-3-methoxy-2-nitropyridine (32). LCMS: purity: 92%; MS (m/z): 233 (MH+).

Workup

  1. extractionextracted with ethyl acetate (3×50 mL)
  2. dry with materialthe organic phase was dried over anhydrous sodium sulfate
  3. customThe solvent was then removed under reduced pressure

Sources & evidence

ORD record
ord-ee7c04f7c5994b9e868cbabfd5b70c21
Source dataset
uspto-grants-2016_02
Patent number
US09248190B2

Reaction notes

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