3-Nitrophenylboronic Acid → 5-Bromo-3-methyl-indol-2-one

HRID 6982

Reaction equation

HRID 6982 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]2[C:8](=[CH:9][CH:10]=1)[NH:7][C:6](=[O:11])[CH:5]2[CH3:12].[N+](C1C=C(B(O)O)C=CC=1)([O-])=O.C(=O)([O-])[O-].[K+].[K+].[Cl-].[NH4+]>C(COC)OC.O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[Br:1][C:2]1[CH:10]=[CH:9][C:8]2[C:4](=[C:5]([CH3:12])[C:6](=[O:11])[N:7]=2)[CH:3]=1

Participants

8

Reactant 4

HCID 16773-Nitrophenylboronic AcidHCID 11430Potassium CarbonateHCID 25517Ammonium ChlorideHCID 120859345-bromo-3-methyl-2,3-dihydro-1H-indol-2-one

Product 1

HCID 220193765-Bromo-3-methyl-indol-2-oneYield 60.3%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolventHCID 80711,2-DimethoxyethaneSolvent

Procedure

5-Bromo-3-methyl-1,3-dihydro-indol-2-one (0.50 g, 2.22 mmol) and tetrakis(triphenylphosphine)palladium(0) (0.15 g) were stirred under an atmosphere of nitrogen in dimethoxyethane (18 cm3). After 15 min., 3-nitrophenyl boronic acid (0.74 g, 4.45 mmol) was added, followed by potassium carbonate (1.86 g, 13.5 mmol) in water (7 cm3). The reaction was heated to reflux for 8 h and then stirred at room temperature overnight. Saturated ammonium chloride was added; and the aqueous layer was extracted with EtOAc (×3). The combined organic layers were dried (MgSO4), filtered, and evaporated. The residue was purified by column chromatography (SiO2, EtOAc: hexane 1:2); eluted: 2:1 hexane; ethyl acetate, to give the title compound (0.30 g, 47%), mp 200–203° C.; 1H NMR (DMSO-d6) δ 1.41 (d, 3H, J=7.61 Hz), 3.50 (q, 1H, J=7.60 Hz), 6.96 (d, 1H, J=8.08 Hz), 7.62 (d, 1H, J=8.06 Hz), 7.75–7.70 (m, 2H), 8.18–8.10 (m, 2H), 8.41–8.39 (m, 1H), 10.5 (s, 1H); IR (KBr) 3450, 1700 cm−1; MS (EI) m/z 267 (M−H); Anal. Calc. for C15H12N2O3+0.2C4H8O2: C, 66.61; H, 4.46; N, 9.83; Found: C, 66.26; H, 4.59; N, 10.06.

Workup

  1. temperatureThe reaction was heated
  2. temperatureto reflux for 8 h
  3. extractionand the aqueous layer was extracted with EtOAc (×3)
  4. dry with materialThe combined organic layers were dried (MgSO4)
  5. filtrationfiltered
  6. customevaporated
  7. customThe residue was purified by column chromatography (SiO2, EtOAc: hexane 1:2)
  8. washeluted

Sources & evidence

ORD record
ord-f1ad471805684fc5b6ebc2d669085dc4
Source dataset
uspto-grants-2006_08
Patent number
US07084168B2

Linked notes

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