Potassium Carbonate → Methyl 8-bromo-4,5-dihydrobenzo[b]thieno[2,3-d]oxepine-2-carboxylate

HRID 84406Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 84406
[Br:1][C:2]1[CH:3]=[CH:4][C:5]2=[C:6]([CH:15]=1)[O:7][CH2:8][CH2:9][C:10]([CH:13]=O)=[C:11]2Cl.C(=O)([O-])[O-].[K+].[K+].[C:22]([O:26][CH3:27])(=[O:25])[CH2:23][SH:24]>CN(C=O)C.O>[Br:1][C:2]1[CH:3]=[CH:4][C:5]2[C:11]3[S:24][C:23]([C:22]([O:26][CH3:27])=[O:25])=[CH:13][C:10]=3[CH2:9][CH2:8][O:7][C:6]=2[CH:15]=1

Komponenten

6

Edukt 3

HCID 11430Potassium CarbonateHCID 16907Methyl ThioglycolateHCID 57900258(Z)-8-bromo-5-chloro-2,3-dihydrobenzo[b]oxepine-4-carbaldehyde

Produkt 1

HCID 56833843Methyl 8-bromo-4,5-dihydrobenzo[b]thieno[2,3-d]oxepine-2-carboxylateAusbeute 78 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 962WaterLösungsmittelHCID 6228DimethylformamideLösungsmittel

Reaktionsbedingungen

Temperatur
50 °C

Versuchsvorschrift

(Z)-8-Bromo-5-chloro-2,3-dihydrobenzo[b]oxepine-4-carbaldehyde 9 was dissolved in 10 mL DMF and treated sequentially with potassium carbonate (2.20 g, 16.6 mmol) and methyl thioglycolate (0.83 mL). The whole was heated at 50° C. overnight, cooled to room temperature, diluted with water and extracted with ethylacetate. The combined organics were washed with brine, dried over sodium sulfate and concentrated. The crude residue was purified by flash column chromatography (20-50% ethylacetate in hexanes) to give 2.20 g (78% yield) as a colorless solid. 1H NMR (DMSO-d6, 500 MHz) 7.70 (s, 1H), 7.67 (d, J=8.5 Hz, 1H), 7.31-7.28 (m, 2H), 4.32 (t, J=5.0 Hz, 2H), 3.84 (s, 3H), 3.21 (t, J=5.0 Hz, 2H).

Aufarbeitung

  1. temperaturecooled to room temperature
  2. extractionextracted with ethylacetate
  3. washThe combined organics were washed with brine
  4. dry with materialdried over sodium sulfate
  5. concentrationconcentrated
  6. customThe crude residue was purified by flash column chromatography (20-50% ethylacetate in hexanes)
  7. customto give 2.20 g (78% yield) as a colorless solid

Quellen und Nachweise

ORD-Eintrag
ord-3601d59b9bef4e99abe634a48f4387dd
Quelldatensatz
uspto-grants-2014_09
Patentnummer
US08846762B2

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