Dimethylformamide → 2,3-Dihydro-8-methoxy-4H-1-benzothiopyran-4-one

HRID 1521815Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1521815
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][C:4]=1[S:9][CH2:10][CH2:11][C:12]([OH:14])=O.C(Cl)(=O)C(Cl)=O.CN(C=O)C.[Sn](Cl)(Cl)(Cl)Cl>C(Cl)Cl>[CH3:1][O:2][C:3]1[CH:8]=[CH:7][CH:6]=[C:5]2[C:4]=1[S:9][CH2:10][CH2:11][C:12]2=[O:14]

Komponenten

6

Edukt 4

HCID 6228DimethylformamideHCID 24287Tin tetrachlorideHCID 65578Oxalyl chlorideHCID 4604295HCID 4604295, Verbindung

Produkt 1

HCID 64553542,3-Dihydro-8-methoxy-4H-1-benzothiopyran-4-oneAusbeute 69,8 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6344DichloromethaneLösungsmittel3×

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

To a solution of 3-[(2-methoxyphenyl)thio]propanoic acid (5.0 g, 23.6 mmol) in dry DCM (50 mL) at 0° C. is added oxalyl chloride (6.01 g, 4.09 mL, 47.2 mmol, 2 Eq) followed by few drops of DMF. The reaction mixture is stirred at 0° C. for 30 minutes. After 30 minutes, the solvent is removed under reduced pressure. To a solution of the acid chloride in DCM (150 mL) at 0° C. is added a solution of tin (IV) chloride in DCM (26 mL, 1 M, 26.0 mmol, 1.1 Eq) and the reaction mixture is stirred for 2 h. The reaction is quenched by addition of water and the product is extracted with DCM. The organic layer is dried over MgSO4, concentrated under reduced pressure. The crude residue is purified by flash chromatography (eluent: ethyl acetate/hexane 4/6) to afford 3.2 g of the title compound as a white solid.1H NMR (DMSO-d6, 400 MHz): δ 7.59-7.57 (m, 1H), 7.18 (m, 2H), 3.84 (s, 3H), 3.24-3.21 (m, 2H), 2.84-2.81 (m, 2H). MS (ESI+): 196.0. HPLC (max plot) 89.4%; Rt 3.36 min.

Aufarbeitung

  1. waitAfter 30 minutes
  2. customthe solvent is removed under reduced pressure
  3. stirringthe reaction mixture is stirred for 2 h
  4. customThe reaction is quenched by addition of water
  5. extractionthe product is extracted with DCM
  6. dry with materialThe organic layer is dried over MgSO4
  7. concentrationconcentrated under reduced pressure
  8. customThe crude residue is purified by flash chromatography (eluent: ethyl acetate/hexane 4/6)

Quellen und Nachweise

ORD-Eintrag
ord-e5c3b7c42fc449cf82588feddb651833
Quelldatensatz
uspto-grants-2015_07
Patentnummer
US09073940B2

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