Ethyl Acetoacetate → Ethyl 4-amino-6-methyl-3-[3-(methyloxy)phenyl]thieno[2,3-b]pyridine-5-carboxylate

HRID 573546Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 573546
[NH2:1][C:2]1[S:3][CH:4]=[C:5]([C:9]2[CH:14]=[CH:13][CH:12]=[C:11]([O:15][CH3:16])[CH:10]=2)[C:6]=1[C:7]#[N:8].[C:17]([O:23][CH2:24][CH3:25])(=[O:22])[CH2:18][C:19]([CH3:21])=O.Cl[Sn](Cl)(Cl)Cl>C1(C)C=CC=CC=1>[NH2:8][C:7]1[C:18]([C:17]([O:23][CH2:24][CH3:25])=[O:22])=[C:19]([CH3:21])[N:1]=[C:2]2[S:3][CH:4]=[C:5]([C:9]3[CH:14]=[CH:13][CH:12]=[C:11]([O:15][CH3:16])[CH:10]=3)[C:6]=12

Komponenten

5

Edukt 3

HCID 8868Ethyl AcetoacetateHCID 24287Tin tetrachlorideHCID 167961562-Amino-4-[3-(methyloxy)phenyl]-3-thiophenecarbonitrile

Produkt 1

HCID 68323793Ethyl 4-amino-6-methyl-3-[3-(methyloxy)phenyl]thieno[2,3-b]pyridine-5-carboxylateAusbeute 61,6 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 1140TolueneLösungsmittel

Versuchsvorschrift

A mixture of 2-amino-4-[3-(methyloxy)phenyl]-3-thiophenecarbonitrile (1 g, 4.34 mmol) (Description 13), ethyl acetoacetate (0.550 mL, 4.34 mmol) and SnCl4 (1.019 mL, 8.68 mmol) in toluene (25 mL) was stirred at RT for 30 min followed by reflux for 3 h. After cooling to RT, the mixture was quenched with 2M NaOH (50 mL) and extracted with ethyl acetate (3×40 mL). The combined organics were washed with brine (50 mL), dried and concentrated. Purification by chromatography on silica gel, eluting with a gradient of 0-50% ethyl acetate in cyclohexane, to give the title compound (915 mg). LCMS (A) m/z: 343 [M+1]+, Rt 1.25 min (acidic).

Aufarbeitung

  1. temperatureby reflux for 3 h
  2. temperatureAfter cooling to RT
  3. customthe mixture was quenched with 2M NaOH (50 mL)
  4. extractionextracted with ethyl acetate (3×40 mL)
  5. washThe combined organics were washed with brine (50 mL)
  6. customdried
  7. concentrationconcentrated
  8. customPurification by chromatography on silica gel
  9. washeluting with a gradient of 0-50% ethyl acetate in cyclohexane

Quellen und Nachweise

ORD-Eintrag
ord-5c4aab08a7ae4938aa1026bbf02f2d4b
Quelldatensatz
uspto-grants-2015_05
Patentnummer
US09029545B2

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