Dimethylformamide → HCID 10881454, compound

HRID 2306011Notes

Reaction equation

HRID 2306011 reaction equation
[OH:1][C:2]1[CH:3]=[C:4]([C:8]2[C:17]3[C:12](=[CH:13][C:14]([O:18][CH3:19])=[CH:15][CH:16]=3)[O:11][C:10](=[O:20])[CH:9]=2)[CH:5]=[CH:6][CH:7]=1.C([O-])([O-])=O.[K+].[K+].CN(C)C=O.[CH2:32](Br)[CH2:33][CH3:34]>C(#N)C>[CH2:32]([O:1][C:2]1[CH:3]=[C:4]([C:8]2[C:17]3[C:12](=[CH:13][C:14]([O:18][CH3:19])=[CH:15][CH:16]=3)[O:11][C:10](=[O:20])[CH:9]=2)[CH:5]=[CH:6][CH:7]=1)[CH2:33][CH3:34]

Participants

6

Reactant 4

HCID 6228DimethylformamideHCID 78401-BromopropaneHCID 11430Potassium CarbonateHCID 18434036HCID 18434036, compound

Product 1

HCID 10881454HCID 10881454, compound

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Conditions

Temperature
98.5 °C

Procedure

4-[3′-(hydroxy)phenyl]-7-methoxycoumarin (1.78 kg) and K2CO3 (1.65 kg) were suspended in acetonitrile (7.20 L) and N,N-dimethylformamide (1.80 L) and the mechanically stirred mixture was heated to 65° C. When the reaction had reached 65° C., neat n-propylbromide (1.48 kg) was added and the mixture was stirred another 21 hours. The slurry was heated to 88-109° C. and concentrated by distillation. When 6.8-7.0 L of distillate had been removed, the slurry was cooled to 40° C. and diluted with water (14.4 L) and stirred while cooling slowly to 20° C. The slurry was filtered to collect the title compound as a pink, amorphous solid, which was washed with water (2.0 L). The air-dried product was recrystallized from a mixture of hexanes (11.9 L) and isopropanol (6.2 L) at 50° C. Filtration at 22° C. gave a very pale pink, crystalline solid which was washed with hexanes (250 mL) and air-dried. Weight=1.70 kg (5.58 mol, 83%). A second crop of product was isolated from the partially concentrated mother liquors; the light pink, crystalline solid weighed 307 g (0.989 mol, 15%).

Workup

  1. customhad reached 65° C.
  2. concentrationconcentrated by distillation
  3. customWhen 6.8-7.0 L of distillate had been removed
  4. temperaturethe slurry was cooled to 40° C.
  5. additiondiluted with water (14.4 L)
  6. stirringstirred
  7. temperaturewhile cooling slowly to 20° C
  8. filtrationThe slurry was filtered
  9. customto collect the title compound as a pink, amorphous solid, which
  10. washwas washed with water (2.0 L)
  11. customThe air-dried product was recrystallized from a mixture of hexanes (11.9 L) and isopropanol (6.2 L) at 50° C
  12. filtrationFiltration at 22° C.
  13. customgave a very pale pink, crystalline solid which
  14. washwas washed with hexanes (250 mL)
  15. customair-dried
  16. customA second crop of product was isolated from the partially concentrated mother liquors

Sources & evidence

ORD record
ord-3e1796687bcf4fbb88fccacab13874c0
Source dataset
uspto-grants-2002_08
Patent number
US06441173B1

Reaction notes

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