Acetic Acid → 4-bromo-7-ethoxycarbonyl-3-fluoro-6,7,8,9-tetrahydro-5H-carbazole-1-carboxylic acid

HRID 523236

Reaktionsgleichung

Reaktionsgleichung von HRID 523236
Cl.[Br:2][C:3]1[C:11]([F:12])=[CH:10][C:6]([C:7]([OH:9])=[O:8])=[C:5]([NH:13]N)[CH:4]=1.O=[C:16]1[CH2:21][CH2:20][CH2:19][CH:18]([C:22]([O:24][CH2:25][CH3:26])=[O:23])[CH2:17]1.C(O)(=O)C>C1(C)C=CC=CC=1>[Br:2][C:3]1[C:11]([F:12])=[CH:10][C:6]([C:7]([OH:9])=[O:8])=[C:5]2[C:4]=1[C:21]1[CH2:20][CH2:19][CH:18]([C:22]([O:24][CH2:25][CH3:26])=[O:23])[CH2:17][C:16]=1[NH:13]2

Komponenten

5

Edukt 3

HCID 176Acetic AcidHCID 118096Ethyl 3-oxocyclohexanecarboxylateHCID 768481964-Bromo-5-fluoro-2-hydrazinylbenzoic acid hydrochloride

Produkt 1

HCID 1177608064-bromo-7-ethoxycarbonyl-3-fluoro-6,7,8,9-tetrahydro-5H-carbazole-1-carboxylic acidAusbeute 46,8 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 1140TolueneLösungsmittel

Reaktionsbedingungen

Temperatur
110 °C

Versuchsvorschrift

A mixture of 4-bromo-5-fluoro-2-hydrazinylbenzoic acid hydrochloride (5.37 g, 18.8 mmol), ethyl 3-oxocyclohexanecarboxylate (3.52 g, 20.7 mmol) and acetic acid (3.23 mL, 56.4 mmol) in toluene (90 mL) was heated at 110° C. for 20 h. The solvent was removed under reduced pressure, and the residue was diluted with toluene (43 mL) and trifluoroacetic acid (11 mL). The mixture was stirred at 90-94° C. overnight. The cooled mixture was diluted with EtOAc, sonicated, and the precipitate was collected by filtration. The filtrate was concentrated and resuspended in EtOAc with sonication, resulting in another precipitate which was also collected by filtration and washed with EtOAc. The combined solids were triturated twice with MeOH to give a solid. The combined filtrates were concentrated and the residue was triturated with MeOH to give additional solid. The solids were combined to give 5-bromo-2-ethoxycarbonyl-6-fluoro-2,3,4,9-tetrahydro-1H-carbazole-8-carboxylic acid as a pale yellow solid (3.38 g). Mass spectrum m/z 384, 386 (M+H)+.

Aufarbeitung

  1. customThe solvent was removed under reduced pressure
  2. additionthe residue was diluted with toluene (43 mL) and trifluoroacetic acid (11 mL)
  3. additionThe cooled mixture was diluted with EtOAc
  4. customsonicated
  5. filtrationthe precipitate was collected by filtration
  6. concentrationThe filtrate was concentrated
  7. customresuspended in EtOAc with sonication
  8. customresulting in another precipitate which
  9. filtrationwas also collected by filtration
  10. washwashed with EtOAc
  11. customThe combined solids were triturated twice with MeOH
  12. customto give a solid
  13. concentrationThe combined filtrates were concentrated
  14. customthe residue was triturated with MeOH
  15. customto give additional solid

Quellen und Nachweise

ORD-Eintrag
ord-ab14656f324b414d845b88d78f516f8e
Quelldatensatz
uspto-grants-2016_05
Patentnummer
US09334290B2

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