N-bromobutanimide → HCID 123226035, compound

HRID 1056988Notes

Reaction equation

HRID 1056988 reaction equation
[F:1][C:2]1[CH:38]=[C:37]([F:39])[CH:36]=[CH:35][C:3]=1[O:4][C:5]1[C:10]([N+:11]([O-:13])=[O:12])=[C:9]([NH:14][CH3:15])[CH:8]=[CH:7][C:6]=1[C:16]1[C:17]2[CH:26]=[N:25][N:24]([CH2:27][O:28][CH2:29][CH2:30][Si:31]([CH3:34])([CH3:33])[CH3:32])[C:18]=2[C:19](=[O:23])[N:20]([CH3:22])[CH:21]=1.[Br:40]N1C(=O)CCC1=O>CN(C)C=O.O.C(OCC)(=O)C>[Br:40][C:8]1[C:9]([NH:14][CH3:15])=[C:10]([N+:11]([O-:13])=[O:12])[C:5]([O:4][C:3]2[CH:35]=[CH:36][C:37]([F:39])=[CH:38][C:2]=2[F:1])=[C:6]([C:16]2[C:17]3[CH:26]=[N:25][N:24]([CH2:27][O:28][CH2:29][CH2:30][Si:31]([CH3:34])([CH3:32])[CH3:33])[C:18]=3[C:19](=[O:23])[N:20]([CH3:22])[CH:21]=2)[CH:7]=1

Participants

6

Reactant 2

HCID 67184N-bromobutanimideHCID 123869477HCID 123869477, compound

Product 1

HCID 123226035HCID 123226035, compoundYield 90%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

A solution of 4-[2-(2,4-difluorophenoxy)-4-(methylamino)-3-nitrophenyl]-6-methyl-1-{[2-(trimethylsilyl)ethoxy]methyl}-1,6-dihydro-7H-pyrazolo[3,4-c]pyridin-7-one (0.433 g, 0.776 mmol) in N,N-dimethylformamide (5.0 mL) was cooled to 0° C. Two portions of N-bromosuccinimide (0.159 g, 0.893 mmol) were added with a 5 min interval to the above solution at 0° C., and the resultant reaction mixture was stirred at 0° C. for 30 min, after which time the reaction mixture was diluted with water and ethyl acetate. Layers were separated and the organic layer was washed with saturated sodium bicarbonate, dried with sodium sulfate, filtered, and concentrated to give a crude residue. Purification by flash column chromatography (100% hexanes to 50% EtOAc/hexanes [EtOAc contained 5% MeOH]) gave the desired product (444 mg, 90%) as a yellow solid. LCMS calculated for C26H29BrF2N5O5Si (M+H)+: m/z=636.1, 638.1. found: 636.0, 638.1.

Workup

  1. customthe resultant reaction mixture
  2. customLayers were separated
  3. washthe organic layer was washed with saturated sodium bicarbonate
  4. dry with materialdried with sodium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customto give a crude residue
  8. customPurification by flash column chromatography (100% hexanes to 50% EtOAc/hexanes [EtOAc contained 5% MeOH])

Sources & evidence

ORD record
ord-e1a9c482631f4a118b0ea93c83229517
Source dataset
uspto-grants-2016_07
Patent number
US09399640B2

Reaction notes

Loading…