Bromine → HCID 21913442, compound

HRID 1352637Notes

Reaction equation

HRID 1352637 reaction equation
C([O-])(=O)C.[K+].[NH2:6][C:7]1[C:12]2[N:13]=[C:14]([CH2:26][CH2:27][CH3:28])[N:15]([CH2:16][CH2:17][O:18][CH2:19][CH2:20][NH:21][S:22]([CH3:25])(=[O:24])=[O:23])[C:11]=2[CH:10]=[CH:9][N:8]=1.[Br:29]Br>C(O)(=O)C>[NH2:6][C:7]1[C:12]2[N:13]=[C:14]([CH2:26][CH2:27][CH3:28])[N:15]([CH2:16][CH2:17][O:18][CH2:19][CH2:20][NH:21][S:22]([CH3:25])(=[O:24])=[O:23])[C:11]=2[C:10]([Br:29])=[CH:9][N:8]=1

Participants

5

Reactant 3

HCID 24408BromineHCID 517044Potassium Acetate2×HCID 21913661HCID 21913661, compound

Product 1

HCID 21913442HCID 21913442, compoundYield 76.7%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

Solid potassium acetate (0.62 g, 6.32 mmol) was added to a solution of N-{2-[2-(4-amino-2-propyl-1H-imidazo[4,5-c]pyridin-1-yl)ethoxy]ethyl}methanesulfonamide (1.8 g, 5.27 mmol) in acetic acid (32 mL). After the potassium acetate had dissolved bromine (1.26 g, 7.91 mmol) was added dropwise. The reaction was stirred at ambient temperature for 40 minutes at which time analysis by thin layer chromatography indicated that the reaction was complete. Excess bromine was quenched by the addition of saturated aqueous sodium bisulfite (˜1 mL). The pH of the reaction mixture was adjusted to pH 7 by the addition of saturated aqueous sodium bicarbonate (100 mL) followed by the addition of solid sodium bicarbonate. The reaction mixture was extracted with dichloromethane (2×100 mL). The combined extracts were washed sequentially with water, saturated aqueous sodium bicarbonate (100 mL) and brine (100 mL), dried over sodium sulfate, filtered and then concentrated under reduced pressure to provide a brown gooey solid. This material was purified by chromatography (silica gel eluting with 95:5 dichloromethane:methanol) to provide 1.7 g of N-{2-[2-(4-amino-7-bromo-2-propyl-1H-imidazo[4,5-c]pyridin-1-yl)ethoxy]ethyl}methanesulfonamide as a white waxy solid, mp 129–131° C.

Workup

  1. additionwas added dropwise
  2. customExcess bromine was quenched by the addition of saturated aqueous sodium bisulfite (˜1 mL)
  3. additionThe pH of the reaction mixture was adjusted to pH 7 by the addition of saturated aqueous sodium bicarbonate (100 mL)
  4. additionfollowed by the addition of solid sodium bicarbonate
  5. extractionThe reaction mixture was extracted with dichloromethane (2×100 mL)
  6. washThe combined extracts were washed sequentially with water, saturated aqueous sodium bicarbonate (100 mL) and brine (100 mL)
  7. dry with materialdried over sodium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated under reduced pressure
  10. customto provide a brown gooey solid
  11. customThis material was purified by chromatography (silica gel eluting with 95:5 dichloromethane:methanol)

Sources & evidence

ORD record
ord-8efd14f98bfc4d588be1fdfbb99aaf38
Source dataset
uspto-grants-2007_05
Patent number
US07220758B2

Reaction notes

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