Water → methyl 2-bromo-5-(pivaloyloxymethyl)-5H-pyrrolo[2,3-b]pyrazine-7-carboxylate

HRID 246568Notes

Reaction equation

HRID 246568 reaction equation
[Br:1][C:2]1[N:3]=[C:4]2[C:10]([C:11]([O:13][CH3:14])=[O:12])=[CH:9][NH:8][C:5]2=[N:6][CH:7]=1.C([O-])([O-])=O.[K+].[K+].[C:21]([O:27][CH2:28]Cl)(=[O:26])[C:22]([CH3:25])([CH3:24])[CH3:23].O>CN(C=O)C>[Br:1][C:2]1[N:3]=[C:4]2[C:10]([C:11]([O:13][CH3:14])=[O:12])=[CH:9][N:8]([CH2:28][O:27][C:21](=[O:26])[C:22]([CH3:25])([CH3:24])[CH3:23])[C:5]2=[N:6][CH:7]=1

Participants

6

Reactant 4

HCID 962WaterHCID 11430Potassium CarbonateHCID 87885Chloromethyl pivalateHCID 86677898methyl 2-bromo-5H-pyrrolo[2,3-b]pyrazine-7-carboxylate

Product 1

HCID 86677991methyl 2-bromo-5-(pivaloyloxymethyl)-5H-pyrrolo[2,3-b]pyrazine-7-carboxylateYield 79.5%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a stirred mixture of methyl 2-bromo-5H-pyrrolo[2,3-b]pyrazine-7-carboxylate (0.24 g, 0.94 mmol) and K2CO3 (0.156 g, 1.13 mmol) in 10 mL of DMF was added chloromethyl pivalate (0.17 g, 1.13 mmol) drop-wise at room temperature. Then the mixture was stirred at room temperature for 16 hours. The mixture was then poured into 30 mL of water, extracted with ethyl acetate (90 mL). The organic phase was washed with brine (10 mL) and dried over Na2SO4 to give a crude product, which was purified by column chromatography (silica gel, 200-300 mesh, eluting with a mixture of ethyl acetate and petroleum ether (1:1, v/v) to give methyl 2-bromo-5-(pivaloyloxymethyl)-5H-pyrrolo[2,3-b]pyrazine-7-carboxylate (0.276 g, 79.5%) as a pale yellow solid. LCMS: (M+H)+=370; 1H NMR (300 MHz, CDCl3): δ 8.42 (s, 1H), 8.38 (s, 1H), 6.21 (s, 2H), 3.96 (s, 3H), 1.15 (s, 9H).

Workup

  1. extractionextracted with ethyl acetate (90 mL)
  2. washThe organic phase was washed with brine (10 mL)
  3. dry with materialdried over Na2SO4
  4. customto give a crude product, which
  5. customwas purified by column chromatography (silica gel, 200-300 mesh
  6. washeluting with a mixture of ethyl acetate and petroleum ether (1:1

Sources & evidence

ORD record
ord-6e27f9cccbd043d48fcde61b3415cd03
Source dataset
uspto-grants-2014_02
Patent number
US08658646B2

Reaction notes

Loading…