Acetic Acid → methyl 5-((4-fluorophenylamino)methyl)-2,2-dimethyl-4H-[1,3]dioxino[4,5-c]pyridine-8-carboxylate

HRID 402570Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 402570
C(O)(=O)C.[CH3:5][O:6][C:7]([C:9]1[N:10]=[CH:11][C:12]([CH:21]=O)=[C:13]2[CH2:18][O:17][C:16]([CH3:20])([CH3:19])[O:15][C:14]=12)=[O:8].[F:23][C:24]1[CH:30]=[CH:29][C:27]([NH2:28])=[CH:26][CH:25]=1.C([BH3-])#N.[Na+]>CO>[F:23][C:24]1[CH:30]=[CH:29][C:27]([NH:28][CH2:21][C:12]2[CH:11]=[N:10][C:9]([C:7]([O:6][CH3:5])=[O:8])=[C:14]3[O:15][C:16]([CH3:19])([CH3:20])[O:17][CH2:18][C:13]=23)=[CH:26][CH:25]=1

Komponenten

6

Edukt 4

HCID 176Acetic AcidHCID 97314-FluoroanilineHCID 5003444Sodium cyanoborohydrideHCID 58360280methyl 5-formyl-2,2-dimethyl-4H-[1,3]dioxino[4,5-c]pyridine-8-carboxylate

Produkt 1

HCID 58360284methyl 5-((4-fluorophenylamino)methyl)-2,2-dimethyl-4H-[1,3]dioxino[4,5-c]pyridine-8-carboxylateAusbeute 96,2 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 887MethanolLösungsmittel

Versuchsvorschrift

Acetic acid (50 μL, 0.87 mmol) was added to a mixture of 5-Formyl-2,2-dimethyl-4H-[1,3]dioxino[4,5-c]pyridine-8-carboxylic acid methyl ester [J. Org. Chem. 1999, 64, 4537] (220 mg, 0.87 mmol) and 4-fluoroaniline (125 μL, 1.3 mmol) in dry methanol (4 mL) and stirred at room temperature for 15 min. and sodium cyanoborohydride (72 mg, 1.3 mmol) was added. This mixture was stirred at room temperature for 3 h followed by evaporation of 90% of the methanol volume under reduced pressure. The residue was extracted with dichloromethane (3×25 mL) and the combined organic layers were dried (anh. Na2SO4), filtered and concentrated under reduced pressure. The crude product was purified by silica gel (methanol/dichloromethane, 0 to 10% methanol) to give 0.290 g of methyl 5-((4-fluorophenylamino)methyl)-2,2-dimethyl-4H-[1,3]dioxino[4,5-c]pyridine-8-carboxylate (compound 21a) (96%) as a white solid MS-ESI m/z 347 [MI-1]+.

Aufarbeitung

  1. stirringThis mixture was stirred at room temperature for 3 h
  2. customfollowed by evaporation of 90% of the methanol volume under reduced pressure
  3. extractionThe residue was extracted with dichloromethane (3×25 mL)
  4. dry with materialthe combined organic layers were dried (anh. Na2SO4)
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure
  7. customThe crude product was purified by silica gel (methanol/dichloromethane, 0 to 10% methanol)

Quellen und Nachweise

ORD-Eintrag
ord-616e42faea6749c2ba1b68b1d3431c79
Quelldatensatz
uspto-grants-2014_06
Patentnummer
US08742123B2

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