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

HRID 573546ノート

反応式

HRID 573546 の反応式
[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

参加物

5

反応物 3

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

生成物 1

HCID 68323793Ethyl 4-amino-6-methyl-3-[3-(methyloxy)phenyl]thieno[2,3-b]pyridine-5-carboxylate収率 61.6%

試薬・触媒・溶媒 1

HCID 1140Toluene溶媒

実験手順

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).

後処理

  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

出典と根拠

ORDレコード
ord-5c4aab08a7ae4938aa1026bbf02f2d4b
出典データセット
uspto-grants-2015_05
特許番号
US09029545B2

反応ノート

読み込み中…