Ethyl Acetoacetate → Ethyl 4-amino-3,6-dimethylthieno[2,3-b]pyridine-5-carboxylate

HRID 573555Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 573555
[NH2:1][C:2]1[S:3][CH:4]=[C:5]([CH3:9])[C:6]=1[C:7]#[N:8].[C:10]([O:16][CH2:17][CH3:18])(=[O:15])[CH2:11][C:12]([CH3:14])=O.Cl[Sn](Cl)(Cl)Cl>C1(C)C=CC=CC=1>[NH2:8][C:7]1[C:11]([C:10]([O:16][CH2:17][CH3:18])=[O:15])=[C:12]([CH3:14])[N:1]=[C:2]2[S:3][CH:4]=[C:5]([CH3:9])[C:6]=12

Komponenten

5

Edukt 3

HCID 8868Ethyl AcetoacetateHCID 24287Tin tetrachlorideHCID 2642812-Amino-4-methylthiophene-3-carbonitrile

Produkt 1

HCID 68323726Ethyl 4-amino-3,6-dimethylthieno[2,3-b]pyridine-5-carboxylateAusbeute 38,6 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 1140TolueneLösungsmittel

Versuchsvorschrift

A mixture of 2-amino-4-methyl-3-thiophenecarbonitrile (300 mg, 2.171 mmol), ethyl acetoacetate (0.275 mL, 2.171 mmol) and SnCl4 (0.510 mL, 434 mmol) in toluene (15 mL) was stirred at RT for 30 min and then reflux for 3.5 h. After cooling to RT, the mixture was quenched with 6M NaOH (20 mL) and extracted with ethyl acetate (3×20 mL). The combined organics were washed with brine (30 mL), dried and concentrated. Purification by chromatography on silica gel, eluting with a gradient of 0-50% ethyl acetate in cyclohexane, afforded the title compound (210 mg). LCMS (A) m/z: 251 [M+1]+, Rt 0.77 min (acidic).

Aufarbeitung

  1. temperaturereflux for 3.5 h
  2. temperatureAfter cooling to RT
  3. customthe mixture was quenched with 6M NaOH (20 mL)
  4. extractionextracted with ethyl acetate (3×20 mL)
  5. washThe combined organics were washed with brine (30 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-4c4c5f8993c744e5b8256fcc68aa764b
Quelldatensatz
uspto-grants-2015_05
Patentnummer
US09029545B2

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