Dimethylformamide → 5-acetyl-3-(N-allyl-N-n-propylamino)chroman

HRID 266627

Reaktionsgleichung

Reaktionsgleichung von HRID 266627
[CH2:1]([N:4]([CH:8]1[CH2:17][C:16]2[C:11](=[CH:12][CH:13]=[CH:14][C:15]=2OS(C(F)(F)F)(=O)=O)[O:10][CH2:9]1)[CH2:5][CH2:6][CH3:7])[CH:2]=[CH2:3].[Li+].[Cl-].[CH3:28][Sn](C)(C)C.CN([CH:36]=[O:37])C>C1COCC1.CCCCCC.Cl[Pd]Cl.C(C1C=C(C)C=C(C(C)(C)C)C=1O)(C)(C)C>[C:36]([C:15]1[CH:14]=[CH:13][CH:12]=[C:11]2[C:16]=1[CH2:17][CH:8]([N:4]([CH2:1][CH:2]=[CH2:3])[CH2:5][CH2:6][CH3:7])[CH2:9][O:10]2)(=[O:37])[CH3:28]

Komponenten

8

Edukt 4

HCID 6228DimethylformamideHCID 11661TetramethyltinHCID 433294Lithium ChlorideHCID 190282203-(N-Allyl-N-n-propylamino)-5-trifluoromethane-sulfonyloxychroman

Produkt 1

HCID 190280895-acetyl-3-(N-allyl-N-n-propylamino)chromanAusbeute 39 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 24290Palladium ChlorideKatalysatorHCID 314042,6-Di-tert-butyl-4-methylphenolKatalysatorHCID 21883165Tetrahydrofuran hexaneLösungsmittel

Reaktionsbedingungen

Temperatur
120 °C

Versuchsvorschrift

3-(N-Allyl-N-n-propylamino)-5-trifluoromethanesulfonyloxychroman (0.28 g, 0.74 mmol), LiCl (0.097 g, 2.3 mmol), PdCl2 (dppf) (0.031 g, 0.04 mmol) and 2.6-di-t-butyl-4-methylphenol (0.005 g) were dissolved in DMF (5.0 mL) in a three-necked round-bottom flask (50 mL) with a magnetic stirrer. The flask was evacuated, followed by inlet of CO (three times). Tetramethyltin (0.12 mL, 0.89 mmol) was added and then the mixture was stirred under an atmosphere of CO (1 atm) at 120° C. (oilbath temp) for 4 hours. The solvent was evaporated, the residue was partitioned between aqueous NH3 (2M) and CH2Cl2 (3×15 mL) and the organic phases were dried (Na2SO4), filtered and concentrated in vacuo. Column chromatography on silica with THF-n-hexane (1:9) as eluent afforded 5-acetyl-3-(N-allyl-N-n-propylamino)chroman (0.078 g, 39% yield) as an oil. The base was precipitated from an ether solution by adding a slight excess of HCl (approx. 3M in ether). The crude salt was collected and dried in vacuo at 40° C. to give a white amorphous powder. Mp 125°-127° C. PdCl2 (dppf)=dichloro[1,1'-bis(diphenylphosphino)ferrocene]-palladium (II).

Aufarbeitung

  1. customThe flask was evacuated
  2. customfollowed by inlet of CO (three times)
  3. customThe solvent was evaporated
  4. customthe residue was partitioned between aqueous NH3 (2M) and CH2Cl2 (3×15 mL)
  5. dry with materialthe organic phases were dried (Na2SO4)
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo

Quellen und Nachweise

ORD-Eintrag
ord-0d1b72e2d3d54b20ab6d9f774b712851
Quelldatensatz
uspto-grants-1997_07
Patentnummer
US05650524

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