Potassium Carbonate → Benzyl 4-[di(ethoxycarbonyl)methoxy]indole-1-carboxylate

HRID 16570

Reaktionsgleichung

Reaktionsgleichung von HRID 16570
[OH:1][C:2]1[CH:10]=[CH:9][CH:8]=[C:7]2[C:3]=1[CH:4]=[CH:5][N:6]2[C:11]([O:13][CH2:14][C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1)=[O:12].C(=O)([O-])[O-].[K+].[K+].Br[CH:28]([C:34]([O:36][CH2:37][CH3:38])=[O:35])[C:29]([O:31][CH2:32][CH3:33])=[O:30]>CC(C)=O>[CH2:37]([O:36][C:34]([CH:28]([C:29]([O:31][CH2:32][CH3:33])=[O:30])[O:1][C:2]1[CH:10]=[CH:9][CH:8]=[C:7]2[C:3]=1[CH:4]=[CH:5][N:6]2[C:11]([O:13][CH2:14][C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1)=[O:12])=[O:35])[CH3:38]

Komponenten

5

Edukt 3

HCID 11430Potassium CarbonateHCID 69637Diethyl bromomalonateHCID 12622101Benzyl 4-hydroxy-1H-indole-1-carboxylate

Produkt 1

HCID 11539127Benzyl 4-[di(ethoxycarbonyl)methoxy]indole-1-carboxylateAusbeute 81,3 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 180AcetoneLösungsmittel

Versuchsvorschrift

The indole 11 (10.69 g, 40 mmol) was added to a suspension of anhydrous potassium carbonate (8.29 g, 60 mmol) in acetone (400 mL) and the mixture was stirred at room temperature for 15 min. Diethyl bromomalonate (11.47 g, 48 mmol) was added and the mixture was heated under reflux for 17 h. The solid was filtered off and washed with acetone and the combined filtrates were evaporated. The residue was dissolved in diethyl ether (150 mL), washed with 0.5 M aq. sodium hydroxide and brine, dried and evaporated to a brown viscous oil (16.87 g). After trituration with diethyl ether, the precipitated white solid was filtered off and the filtrate was evaporated. The residue was flash chromatographed [ethyl acetate-hexanes (15:85)] to give more solid and the combined solids were recrystallised to give 12 as white crystals (13.83 g, 81%), mp 77-78° C. (from ethyl acetate-hexanes); 1H NMR (500 MHz) δ 7.86-7.92 (br d, 1H), 7.57 (d, J=3.7 Hz, 1H), 7.47-7.49 (m, 2H), 7.36-7.43 (m, 3H), 7.20 (t, J=8.1 Hz, 1H), 6.86 (d, J=3.9 Hz, 1H), 6.63 (d, J=8.1 Hz, 1H), 5.45 (s, 2H), 5.30 (s, 1H), 4.29-4.37 (m, 4H), 1.30 (t, J=7.1 Hz, 6H). Anal. Calcd for C23H23NO7: C, 64.93; H, 5.45; N, 3.29. Found: C, 65.06; H, 5.64; N, 3.21.

Aufarbeitung

  1. temperaturethe mixture was heated
  2. temperatureunder reflux for 17 h
  3. filtrationThe solid was filtered off
  4. washwashed with acetone
  5. customthe combined filtrates were evaporated
  6. dissolutionThe residue was dissolved in diethyl ether (150 mL)
  7. washwashed with 0.5 M aq. sodium hydroxide and brine
  8. customdried
  9. customevaporated to a brown viscous oil (16.87 g)
  10. filtrationAfter trituration with diethyl ether, the precipitated white solid was filtered off
  11. customthe filtrate was evaporated
  12. customchromatographed [ethyl acetate-hexanes (15:85)]
  13. customto give more solid
  14. customthe combined solids were recrystallised

Quellen und Nachweise

ORD-Eintrag
ord-77be926e24c642fcad0552c61267bc7f
Quelldatensatz
uspto-grants-2010_06
Patentnummer
US07737169B2

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