Bromine → Methyl 3-bromo-9H-pyrrolo[2,3-b:5,4-c']dipyridine-6-carboxylate

HRID 1888371Notes

Reaction equation

HRID 1888371 reaction equation
[Br:1]Br.[CH3:3][O:4][C:5]([C:7]1[N:15]=[CH:14][C:13]2[NH:12][C:11]3[N:16]=[CH:17][CH:18]=[CH:19][C:10]=3[C:9]=2[CH:8]=1)=[O:6].C([O-])(=O)C.[Na+]>C(O)(=O)C>[CH3:3][O:4][C:5]([C:7]1[N:15]=[CH:14][C:13]2[NH:12][C:11]3[N:16]=[CH:17][C:18]([Br:1])=[CH:19][C:10]=3[C:9]=2[CH:8]=1)=[O:6]

Participants

5

Reactant 3

HCID 24408BromineHCID 517045Sodium AcetateHCID 44436456Methyl 9H-pyrrolo[2,3-b:5,4-c']dipyridine-6-carboxylate

Product 1

HCID 58266719Methyl 3-bromo-9H-pyrrolo[2,3-b:5,4-c']dipyridine-6-carboxylateYield 103.9%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Conditions

Temperature
100 °C

Procedure

Bromine (6.76 ml, 132.0 mmol) was added to a mixture of 9H-dipyrido[2,3-b;4′,3′-d]pyrrole-6-carboxylic acid methyl ester (10.0 g, 44.0 mmol) and sodium acetate (11.2 g, 136.4 mmol) in acetic acid (360 mL) and then the reaction mixture was heated at 100° C. for 90 minutes. The reaction mixture was then cooled to ambient temperature and the solvent removed under reduced pressure then the residue was treated with saturated sodium thiosulfate solution (40 mL) followed by water (100 mL) and then the pH of the aqueous solution was adjusted to 7 by the addition of saturated sodium hydrogen carbonate solution. The resultant precipitate was collected by filtration and the solid was washed with water (20 mL) then dried at 60° C. until constant weight was achieved, to afford the desired material as an off-white solid (14.0 g, quantitative yield). 1H NMR (DMSO-D6, 300 MHz): 9.13 (d, J=2.3 Hz, 1H), 9.00 (d, J=2.0 Hz, 2H), 8.70 (d, J=2.3 Hz, 1H), 3.92 (s, 3H). LCMS (Method B): RT=2.92 min, M+H+=306/308.

Workup

  1. temperatureThe reaction mixture was then cooled to ambient temperature
  2. customthe solvent removed under reduced pressure
  3. additionthe residue was treated with saturated sodium thiosulfate solution (40 mL)
  4. additionthe pH of the aqueous solution was adjusted to 7 by the addition of saturated sodium hydrogen carbonate solution
  5. filtrationThe resultant precipitate was collected by filtration
  6. washthe solid was washed with water (20 mL)
  7. customthen dried at 60° C. until constant weight

Sources & evidence

ORD record
ord-082c8d08111d42418e4d09d4b80d85a5
Source dataset
uspto-grants-2013_08
Patent number
US08501765B2

Reaction notes

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