Bicarbonate Ion → (3-Amino-2,6-difluoro-phenyl)-(5-methyl-1H-pyrrolo[2,3-b]pyridin-3-yl)-methanone

HRID 217591Notes

Reaction equation

HRID 217591 reaction equation
[F:1][C:2]1[C:7]([N+:8]([O-])=O)=[CH:6][CH:5]=[C:4]([F:11])[C:3]=1[C:12]([C:14]1[C:22]2[C:17](=[N:18][CH:19]=[C:20]([CH3:23])[CH:21]=2)[NH:16][CH:15]=1)=[O:13].C(OCC)(=O)C.C(=O)(O)[O-]>O>[NH2:8][C:7]1[C:2]([F:1])=[C:3]([C:12]([C:14]2[C:22]3[C:17](=[N:18][CH:19]=[C:20]([CH3:23])[CH:21]=3)[NH:16][CH:15]=2)=[O:13])[C:4]([F:11])=[CH:5][CH:6]=1

Participants

5

Reactant 3

HCID 769Bicarbonate IonHCID 8857Ethyl AcetateHCID 59569621(2,6-difluoro-3-nitro-phenyl)-(5-methyl-1H-pyrrolo[2,3-b]pyridin-3-yl)-methanone

Product 1

HCID 58086440(3-Amino-2,6-difluoro-phenyl)-(5-methyl-1H-pyrrolo[2,3-b]pyridin-3-yl)-methanone

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
65 °C

Procedure

To (2,6-difluoro-3-nitro-phenyl)-(5-methyl-1H-pyrrolo[2,3-b]pyridin-3-yl)-methanone (16, 1.165 g, 3.672 mmol), 80 mL of ethyl acetate was added, followed by stannous chloride, dihydrate (2.86 g, 12.6 mmol). The suspension was stirred in an oil bath at 65° C. for 18 hours, then poured into a beaker with 200 mL each of water and saturated bicarbonate. The resulting milky suspension was treated with celite, then vacuum filtered through a thin pad of celite. The resulting clear layers of the filtrate were separated and the solvents were removed from the ethyl acetate layer. The resulting material was purified by silica gel column chromatography eluting with a gradient from 30 to 100% ethyl acetate in hexanes to give the desired compound with some impurities. This material was re-purified by silica gel column chromatography eluting with a gradient from 1 to 60% methanol in dichloromethante to give the desired compound (17, 760 mg). 1H NMR was consistent with the desired compound structure. MS (ESI) [M+H+]+=288.5.

Workup

  1. additionThe resulting milky suspension was treated with celite
  2. filtrationvacuum filtered through a thin pad of celite
  3. customThe resulting clear layers of the filtrate were separated
  4. customthe solvents were removed from the ethyl acetate layer
  5. customThe resulting material was purified by silica gel column chromatography
  6. washeluting with a gradient from 30 to 100% ethyl acetate in hexanes

Sources & evidence

ORD record
ord-a60c3721d71e40fcb615bd662f32f807
Source dataset
uspto-grants-2012_06
Patent number
US08198273B2

Reaction notes

Loading…