Potassium Carbonate → 3-(1,3-Benzodioxol-5-yl)-6-propoxy-1H-inden-1-one

HRID 277489Notes

Reaction equation

HRID 277489 reaction equation
C([O-])([O-])=O.[K+].[K+].[O:7]1[C:11]2[CH:12]=[CH:13][C:14]([CH:16]=[CH:17][C:18]([C:20]3[CH:25]=[C:24]([O:26][CH2:27][CH2:28][CH3:29])[CH:23]=[CH:22][C:21]=3Br)=[O:19])=[CH:15][C:10]=2[O:9][CH2:8]1>Cl[Pd]Cl.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.CN(C=O)C>[O:7]1[C:11]2[CH:12]=[CH:13][C:14]([C:16]3[C:21]4[C:20](=[CH:25][C:24]([O:26][CH2:27][CH2:28][CH3:29])=[CH:23][CH:22]=4)[C:18](=[O:19])[CH:17]=3)=[CH:15][C:10]=2[O:9][CH2:8]1

Participants

6

Reactant 2

HCID 11430Potassium CarbonateHCID 542642933-(1,3-Benzodioxol-5-yl)-1-(2-bromo-5-propoxyphenyl)-2-propen-1-one

Product 1

HCID 118089983-(1,3-Benzodioxol-5-yl)-6-propoxy-1H-inden-1-oneYield 73%

Reagents, catalysts & solvents 3

HCID 11776TriphenylphosphineCatalystHCID 24290Palladium ChlorideCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
110 °C

Procedure

A 1 L three-necked flask equipped with mechanical stirrer was charged with DMF (1.5 L), PPh3 (3.6 g, 13.7 mmol), K2CO3 (67.5 g, 0.489 mol), PdCl2 (0.855 g, 4.82 mmol) and 3-(1,3-Benzodioxol-5-yl)-1-(2-bromo-5-propoxyphenyl)-2-propen-1-one (75 g, 0.193 mol). Upon purging the solution with nitrogen, heat the mixture at 110 ° C. for 0.5 h, cool to 40° C.,concentrate to ½ volume (57° C., 40 mm Hg), and add H2O (750 ml) and stir the reaction mixture at room temperature for 1 h. Filter the precipitate and wash with H2O (500 mL). Transfer the wet solid (62 g) to a 1 L 3-necked flask, add EtOAc (500 ml) and 20% KSCN solution (250 mL) and heat the biphasic mixture to 65° C. for 1 h. Remove the aqueous layer, wash the organic layer with brine (2×250 mL), dry over MgSO4 and concentrate in vacuo. Slurry the crude solid in iPrOAc/iPrOH (200 ml, 1:1) and stir for 1.5 h at 5° C. Filter the product, wash with cold iPrOH (50 ml, 0° C.) and air dry to afford 3-(1,3-Benzodioxol-5-yl) -6-propoxy-1H-inden-1-one as an orange solid (43 g, 73% yield): mp 99.0-101.0° C.; 1H NMR δ7.3-7.2 (m, 3H), 7.1 (m, 2H), 6.9 (d, J=8.1 Hz, 1H), 6.75 (dd, J=2.5 8.2 Hz, 1H), 6.05 (s, 1H), 5.8 (s, 1H), 3.95 (t, J=6.6 Hz, 2H), 1.8 (quintet, Hz, 2H), 1.05 (t, J=7.4 Hz, 3H).

Workup

  1. customA 1 L three-necked flask equipped with mechanical stirrer
  2. customUpon purging the solution with nitrogen
  3. temperaturecool to 40° C.
  4. concentrationconcentrate to ½ volume (57° C., 40 mm Hg)
  5. additionadd H2O (750 ml)
  6. filtrationFilter the precipitate
  7. washwash with H2O (500 mL)
  8. additionTransfer the wet solid (62 g) to a 1 L 3-necked flask, add EtOAc (500 ml) and 20% KSCN solution (250 mL)
  9. temperatureheat the biphasic mixture to 65° C. for 1 h
  10. customRemove the aqueous layer
  11. washwash the organic layer with brine (2×250 mL)
  12. dry with materialdry over MgSO4
  13. concentrationconcentrate in vacuo
  14. stirringstir for 1.5 h at 5° C
  15. filtrationFilter the product
  16. washwash with cold iPrOH (50 ml, 0° C.) and air
  17. customdry

Sources & evidence

ORD record
ord-2003b10d5745415da7e5735be570800c
Source dataset
uspto-grants-2002_03
Patent number
US06355813B1

Reaction notes

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