Water → 3,3-Dibromo-4-chloro-1H-pyrrolo[2,3-b]pyridin-2(3H)-one

HRID 2361103Notes

Reaction equation

HRID 2361103 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][N:5]=[C:4]2[NH:8][CH:9]=[CH:10][C:3]=12.CC(O)(C)C.[Br-:16].[Br-:17].[Br-].[NH+]1C=CC=CC=1.[NH+]1C=CC=CC=1.[NH+]1C=CC=CC=1.[OH2:37]>CCOC(C)=O>[Br:16][C:10]1([Br:17])[C:3]2[C:4](=[N:5][CH:6]=[CH:7][C:2]=2[Cl:1])[NH:8][C:9]1=[O:37]

Participants

6

Reactant 4

HCID 962WaterHCID 6386tert-ButanolHCID 113894934-Chloro-1H-pyrrolo[2,3-b]pyridineHCID 21124087Pyridiniumtribromide3×

Product 1

HCID 223909813,3-Dibromo-4-chloro-1H-pyrrolo[2,3-b]pyridin-2(3H)-one

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Procedure

The title compound was prepared according to the procedure described in WO2001046196A1. To a stirred suspension of 4-chloro-1H-pyrrolo[2,3-b]pyridine (2.00 g, 13.1 mmol) in t-BuOH (131 ml, 13.1 mmol) was added pyridinium tribromide (14.1 g, 44.2 mmol) by small portions. The solution was stirred at rt for 2 h. After 3 h, LCMS showed product and mono brominated product. 5.00 g of pyridinium tribromide was added. After 1.5 h, LCMS showed mainly product and excess pyridinium tribromide. After another 0.5 h, water was added and the whole was diluted with EtOAc until all solids were dissolved. The product was extracted with EtOAc. The organic layer was washed with brine, dried over MgSO4, filtered, and concentrated. Trituration of the crude product with hexanes gave an orange solid. 1H NMR confirmed the product, 3,3-dibromo-4-chloro-1H-pyrrolo[2,3-b]pyridin-2(3H)-one (4.07 g, 95% yield). The product was insoluble in DCM and CHCl3. MS Calcd for C7H3Br2ClN2O: [M]1=324. Found: [M+H]+=325, [M+3H]+=327.

Workup

  1. waitAfter 3 h
  2. waitAfter 1.5 h
  3. waitAfter another 0.5 h
  4. dissolutionwere dissolved
  5. extractionThe product was extracted with EtOAc
  6. washThe organic layer was washed with brine
  7. dry with materialdried over MgSO4
  8. filtrationfiltered
  9. concentrationconcentrated

Sources & evidence

ORD record
ord-a686324dd276415283f580f795dcff0f
Source dataset
uspto-grants-2014_04
Patent number
US08686155B2

Reaction notes

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