4-Aminobenzoic Acid → Ameltolide

HRID 1428868

Reaktionsgleichung

Reaktionsgleichung von HRID 1428868
C(Cl)(=O)C(Cl)=O.CN(C=O)C.[NH2:12][C:13]1[CH:21]=[CH:20][C:16]([C:17]([OH:19])=O)=[CH:15][CH:14]=1.N1C=CC=CC=1.[CH3:28][C:29]1[CH:34]=[CH:33][CH:32]=[C:31]([CH3:35])[C:30]=1[NH2:36].C(N)CN>C(Cl)Cl>[NH2:12][C:13]1[CH:14]=[CH:15][C:16]([C:17]([NH:36][C:30]2[C:31]([CH3:35])=[CH:32][CH:33]=[CH:34][C:29]=2[CH3:28])=[O:19])=[CH:20][CH:21]=1

Komponenten

8

Edukt 6

HCID 9784-Aminobenzoic AcidHCID 1049PyridineHCID 3301EthylenediamineHCID 6228DimethylformamideHCID 68962,6-DimethylanilineHCID 65578Oxalyl chloride

Produkt 1

HCID 13086AmeltolideAusbeute 72,7 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6344DichloromethaneLösungsmittel2×

Versuchsvorschrift

Oxalyl chloride (1.9 mL, 22 mmol) was added dropwise to a solution of DMF (1.7 mL, 22 mmol) and DCM (22 mL) that was kept at 0° C. The resulting foamy white suspension was stirred for 30 min and allowed to warm to room temperature, then cooled again to 0° C. 4-Aminobenzoic acid (1.50 g, 10.9 mmol) was added and the reaction mixture was stirred at room temperature for 1 h. The flask was again cooled to 0° C. and DCM (11 mL) and pyridine (2.6 mL, 33 mmol) were added. Stirring was continued for 50 min and 2,6-dimethyl-phenylamine (1.33 g, 10.9 mmol) was then added. The reaction mixture was stirred at room temperature for 1.5 h and concentrated to dryness. The residue was dissolved in ethanol (30 mL) and 1,2-ethylenediamine (3.3 mL, 49 mmol) was added. The reaction mixture was heated at reflux for 2 h, allowed to cool to room temperature, stirred for 2 d, and concentrated. Water (50 mL) was added to the residue and the precipitate was collected, rinsed well with water, and dried to yield the titled compound (1.904 g, 70% yield). MS (ESI/Cl): mass calcd. for C15H16N2O, 240.1; m/z found, 241.1 [M+H]+. 1H NMR (400 MHz, CD3OD): 7.76 (d, J=8.8 Hz, 2H), 7.10 (s, 3H), 6.72 (d, J=8.8 Hz, 2H), 2.24 (s, 6H).

Aufarbeitung

  1. customwas kept at 0° C
  2. temperaturecooled again to 0° C
  3. stirringthe reaction mixture was stirred at room temperature for 1 h
  4. temperatureThe flask was again cooled to 0° C.
  5. stirringStirring
  6. waitwas continued for 50 min
  7. stirringThe reaction mixture was stirred at room temperature for 1.5 h
  8. concentrationconcentrated to dryness
  9. dissolutionThe residue was dissolved in ethanol (30 mL)
  10. temperatureThe reaction mixture was heated
  11. temperatureat reflux for 2 h
  12. temperatureto cool to room temperature
  13. stirringstirred for 2 d
  14. concentrationconcentrated
  15. additionWater (50 mL) was added to the residue
  16. customthe precipitate was collected
  17. washrinsed well with water
  18. customdried

Quellen und Nachweise

ORD-Eintrag
ord-c1ba85ab04744ab6954e5c61f54177ee
Quelldatensatz
uspto-grants-2015_01
Patentnummer
US08937078B2

Verknüpfte Notizen

Wird geladen…