Methanol → HCID 59375101, Verbindung

HRID 1811109Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1811109
[C:1]([C:4]1[CH:5]=[CH:6][C:7]([C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][C:23]=2[F:28])=[C:8]2[C:16]=1[NH:15][C:14]1[CH:13]=[C:12]([C:17](OCC)=[O:18])[CH:11]=[CH:10][C:9]2=1)(=[O:3])[NH2:2].[H-].[Al+3].[Li+].[H-].[H-].[H-].CO.C(O)(C(F)(F)F)=O>C1COCC1.CCOC(C)=O>[F:28][C:23]1[CH:24]=[CH:25][CH:26]=[CH:27][C:22]=1[C:7]1[C:8]2[C:9]3[C:14](=[CH:13][C:12]([CH2:17][OH:18])=[CH:11][CH:10]=3)[NH:15][C:16]=2[C:4]([C:1]([NH2:2])=[O:3])=[CH:5][CH:6]=1

Komponenten

7

Edukt 4

HCID 887MethanolHCID 6422Trifluoroacetic acidHCID 21226445Aluminium lithium hydride2×HCID 59375158HCID 59375158, Verbindung

Produkt 1

HCID 59375101HCID 59375101, VerbindungAusbeute 108,4 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 8028TetrahydrofuranLösungsmittelHCID 8857Ethyl AcetateLösungsmittel

Versuchsvorschrift

A solution of ethyl 8-carbamoyl-5-(2-fluorophenyl)-9H-carbazole-2-carboxylate (Example 3-12, 0.81 g, 2.152 mmol) in THF (26.9 mL) at 0° C. was treated with lithium aluminum hydride (1.0 M in THF, 3.01 mL, 3.01 mmol), and the mixture was stirred at rt for 5 h. Additional lithium aluminum hydride (1.3 mL, 1.3 mmol) was added and the mixture was stirred at rt overnight. The mixture was treated with methanol and TFA and diluted with EtOAc, washed with brine, dried and concentrated to provide impure 4-(2-fluorophenyl)-7-(hydroxymethyl)-9H-carbazole-1-carboxamide (0.78 g) contaminated with starting material. A small amount was purified by preparative HPLC to provide 4-(2-fluorophenyl)-7-(hydroxymethyl)-9H-carbazole-1-carboxamide, isolated as the TFA salt. 1H NMR (500 MHz, methanol-d4) δ 7.82 (1 H, d, J=7.8 Hz), 7.51 (1 H, s), 7.44-7.50 (1 H, m), 7.42 (1 H, td, J=7.5, 1.9 Hz), 7.25-7.30 (1 H, m), 7.22 (1 H, t, J=9.2 Hz), 7.05 (1 H, d, J=8.3 Hz), 6.99 (1 H, d, J=7.8 Hz), 6.85 (1 H, dd, J=8.0, 1.4 Hz), 4.62 (2 H, s). Mass spectrum m/z 334.9 (M+H)+.

Aufarbeitung

  1. stirringthe mixture was stirred at rt overnight
  2. washwashed with brine
  3. customdried
  4. concentrationconcentrated

Quellen und Nachweise

ORD-Eintrag
ord-62344ff2912841d6ba277099a7f12f8e
Quelldatensatz
uspto-grants-2013_01
Patentnummer
US08362065B2

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