Water → 3-Bromomethyl-7-(2,6-difluorobenzyl)-4,7-dihydro-5-isobutyryl-2-(4-nitrophenyl)-4-oxothieno[2,3-b]pyridine

HRID 2304876Notes

Reaction equation

HRID 2304876 reaction equation
[Br:1][CH2:2][C:3]1[C:11]2[C:10](=[O:12])[C:9]([C:13](=[O:17])[CH:14]([CH3:16])[CH3:15])=[CH:8][N:7]([CH2:18][C:19]3[C:24]([F:25])=[CH:23][CH:22]=[CH:21][C:20]=3[F:26])[C:6]=2[S:5][C:4]=1[C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1.[N+:33]([O-])([O-:35])=[O:34].[Na+].O>CS(O)(=O)=O.C(OCC)(=O)C>[Br:1][CH2:2][C:3]1[C:11]2[C:10](=[O:12])[C:9]([C:13](=[O:17])[CH:14]([CH3:16])[CH3:15])=[CH:8][N:7]([CH2:18][C:19]3[C:20]([F:26])=[CH:21][CH:22]=[CH:23][C:24]=3[F:25])[C:6]=2[S:5][C:4]=1[C:27]1[CH:32]=[CH:31][C:30]([N+:33]([O-:35])=[O:34])=[CH:29][CH:28]=1

Participants

6

Reactant 3

HCID 962WaterHCID 24268Sodium NitrateHCID 184586143-Bromomethyl-7-(2,6-difluorobenzyl)-4,7-dihydro-5-isobutyryl-4-oxo-2-phenylthieno[2,3-b]pyridine

Product 1

HCID 155504633-Bromomethyl-7-(2,6-difluorobenzyl)-4,7-dihydro-5-isobutyryl-2-(4-nitrophenyl)-4-oxothieno[2,3-b]pyridineYield 59.5%

Reagents, catalysts & solvents 2

HCID 6395Methanesulfonic AcidSolvent2×HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
11 °C

Procedure

The compound obtained in Example 16 (1 g) was dissolved in methanesulfonic acid (5 ml) with cooling at 10 to 12° C. and then treated dropwise with a solution of sodium nitrate (0.165 g) in methanesulfonic acid (2.5 ml). The mixture was stirred as it was for 2 hours, and then poured into a cool water, and the crystal precipitated was recovered by a filtration, washed with water and diisopropylether, dried in vacuo to obtain a crude crystal (1.04 g). This was suspended in ethyl acetate (15 ml) with stirring and then cooled on ice, and the crystal precipitated was recovered by a filtration, washed with a cool ethyl acetate to obtain the title compound (0.647 g, 59.5%).

Workup

  1. customthe crystal precipitated
  2. filtrationwas recovered by a filtration
  3. washwashed with water and diisopropylether
  4. customdried in vacuo
  5. customto obtain a crude crystal (1.04 g)
  6. stirringwith stirring
  7. temperaturecooled on ice
  8. customthe crystal precipitated
  9. filtrationwas recovered by a filtration
  10. washwashed with a cool ethyl acetate

Sources & evidence

ORD record
ord-7002575a48054182ae6141cab560ca5b
Source dataset
uspto-grants-2002_08
Patent number
US06437132B2

Reaction notes

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