Sesamol → 4-bromo-3-hydroxy-3-(6-hydroxy-1,3-benzodioxol-5-yl)-1-pentyl-1,3-dihydro-2H-indol-2-one

HRID 425444Notes

Reaction equation

HRID 425444 reaction equation
[O:1]1[C:5]2[CH:6]=[CH:7][C:8]([OH:10])=[CH:9][C:4]=2[O:3][CH2:2]1.C([Mg]Cl)(C)C.[Br:16][C:17]1[CH:25]=[CH:24][CH:23]=[C:22]2[C:18]=1[C:19](=[O:32])[C:20](=[O:31])[N:21]2[CH2:26][CH2:27][CH2:28][CH2:29][CH3:30]>O1CCCC1.ClCCl>[Br:16][C:17]1[CH:25]=[CH:24][CH:23]=[C:22]2[C:18]=1[C:19]([OH:32])([C:7]1[C:8]([OH:10])=[CH:9][C:4]3[O:3][CH2:2][O:1][C:5]=3[CH:6]=1)[C:20](=[O:31])[N:21]2[CH2:26][CH2:27][CH2:28][CH2:29][CH3:30]

Participants

6

Reactant 3

HCID 68289SesamolHCID 284924584-bromo-1-pentyl-1H-indole-2,3-dioneHCID 178418918HCID 178418918, compound

Product 1

HCID 120044004-bromo-3-hydroxy-3-(6-hydroxy-1,3-benzodioxol-5-yl)-1-pentyl-1,3-dihydro-2H-indol-2-oneYield 97%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of 1,3-benzodioxol-5-ol (12.8 g, 92.9 mmol) in tetrahydrofuran (200 mL) was added isopropylmagnesium chloride solution (50.7 mL, 101 mmol, 2.0 M in ether) at 0° C. The reaction mixture was stirred at 0° C. for 0.5 h, upon which time the colorless precipitate was formed. After the solvent was removed under reduced pressure, the residue was dissolved in methylene chloride (100 mL) and added to a solution of 4-bromo-1-pentyl-1H-indole-2,3-dione (25.0 g, 84.5 mmol) in dichloromethane (100 mL) via a canula over 10 min at 0° C. The reaction mixture was stirred at ambient temperature for 16 h, quenched with saturated ammonium chloride solution (100 mL) and the organic layer was separated. The aqueous layer was extracted with dichloromethane (100 mL). The combined organic layers was washed with brine, dried over anhydrous sodium sulfate and filtered. The filtrate was concentrated in vacuo to dryness. The residue was subjected to column chromatography eluting with ethyl acetate-hexane to give the title compound (34.9 g, 97%) as a brown gummy material: 1H NMR (300 MHz, DMSO-d6) δ 8.95 (s, 1H), 7.29-7.21 (m, 2H), 6.88-6.81 (m, 1H), 6.55, (s, 1H), 6.14 (s, 1H), 5.86 (dd, 2H), 4.24 (s, 1H), 3.70-3.52 (m, 2H), 1.69-1.55 (m, 2H), 1.31-1.24 (m, 4H), 0.83 (t, 3H); 13C NMR (75 MHz, DMSO-d6) δ 177.6, 152.6, 149.1, 144.8, 141.2, 131.7, 127.7, 127.6, 121.0, 113.8, 108.3, 106.7, 101.7, 101.4, 80.5 40.5, 28.8, 26.7 22.2, 13.9.

Workup

  1. customwas formed
  2. customAfter the solvent was removed under reduced pressure
  3. dissolutionthe residue was dissolved in methylene chloride (100 mL)
  4. stirringThe reaction mixture was stirred at ambient temperature for 16 h
  5. customquenched with saturated ammonium chloride solution (100 mL)
  6. customthe organic layer was separated
  7. extractionThe aqueous layer was extracted with dichloromethane (100 mL)
  8. washThe combined organic layers was washed with brine
  9. dry with materialdried over anhydrous sodium sulfate
  10. filtrationfiltered
  11. concentrationThe filtrate was concentrated in vacuo to dryness
  12. washeluting with ethyl acetate-hexane

Sources & evidence

ORD record
ord-80739769a65b45e98f1c9c5c9dafe4f1
Source dataset
uspto-grants-2012_01
Patent number
US08106087B2

Reaction notes

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