N-bromobutanimide → 5-Bromo-1,3-dihydro-4-methyl-2H-indol-2-one

HRID 1019110Notes

Reaction equation

HRID 1019110 reaction equation
[CH3:1][C:2]1[CH:10]=[CH:9][CH:8]=[C:7]2[C:3]=1[CH2:4][C:5](=[O:11])[NH:6]2.[Br:12]N1C(=O)CCC1=O.C(OCC)(=O)C.CCCCCC>C(#N)C>[Br:12][C:10]1[C:2]([CH3:1])=[C:3]2[C:7](=[CH:8][CH:9]=1)[NH:6][C:5](=[O:11])[CH2:4]2

Participants

5

Reactant 3

HCID 67184N-bromobutanimide2×HCID 125793824-Methyl-1,3-dihydro-2H-indol-2-oneHCID 21226206Ethyl acetate hexane

Product 1

HCID 120432695-Bromo-1,3-dihydro-4-methyl-2H-indol-2-oneYield 21.7%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

4-Methyl-2-oxindole (5 g) in 40 mL of acetonitrile was treated with 7.26 g of N-bromosuccinimide and stirred at room temperature for 4 hours. Thin layer chromatography (ethyl acetate:hexane 1:2, silica gel) showed a mixture of 5-bromo (Rf 0.3) and 5,7-dibromo (Rf 0.5) products. Another 7.26 g of N-bromosuccinimide was added and the mixture stirred for 4 additional hours. The solid was collected by vacuum filtration, washed with 20 mL of acetonitrile and dried to give a 1:1 mixture of mono and dibromo compounds. The filtrate was concentrated and chromatographed on silica gel (ethyl acetate:hexane (1:2)) to give 1.67 g of 5-bromo-4-methyl-2-oxindole as a beige solid. The remaining 1:1 mixture of solids was recrystallized twice from glacial acetic acid to give 3.2 g of 5,7-dibromo-4-methyl-2-oxindole as a light orange solid. The filtrates from this material were chromatographed as above to give 0.6 g of 5-bromo-4-methyl-2-oxindole and 0.5 g of 5,7-dibromo-4-methyl-2-oxindole.

Workup

  1. additiona mixture of 5-bromo (Rf 0.3) and 5,7-dibromo (Rf 0.5) products
  2. stirringthe mixture stirred for 4 additional hours
  3. filtrationThe solid was collected by vacuum filtration
  4. washwashed with 20 mL of acetonitrile
  5. customdried
  6. customto give
  7. concentrationThe filtrate was concentrated
  8. customchromatographed on silica gel (ethyl acetate:hexane (1:2))

Sources & evidence

ORD record
ord-e41301f32cfe476996b7af6f31211d76
Source dataset
uspto-grants-2002_11
Patent number
US06486185B1

Reaction notes

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