Ammonium Chloride → 4-methoxy-6-(1-methyl-3,6-dihydro-2H-pyridin-4-yl)-N'-(4-pyrazolo[1,5-a]pyridin-3-ylpyrimidin-2-yl)benzene-1,3-diamine

HRID 1842803ノート

反応式

HRID 1842803 の反応式
[CH3:1][O:2][C:3]1[CH:8]=[C:7]([C:9]2[CH2:10][CH2:11][N:12]([CH3:15])[CH2:13][CH:14]=2)[C:6]([N+:16]([O-])=O)=[CH:5][C:4]=1[NH:19][C:20]1[N:25]=[C:24]([C:26]2[CH:27]=[N:28][N:29]3[CH:34]=[CH:33][CH:32]=[CH:31][C:30]=23)[CH:23]=[CH:22][N:21]=1.[NH4+].[Cl-]>[Fe].O>[CH3:1][O:2][C:3]1[CH:8]=[C:7]([C:9]2[CH2:10][CH2:11][N:12]([CH3:15])[CH2:13][CH:14]=2)[C:6]([NH2:16])=[CH:5][C:4]=1[NH:19][C:20]1[N:25]=[C:24]([C:26]2[CH:27]=[N:28][N:29]3[CH:34]=[CH:33][CH:32]=[CH:31][C:30]=23)[CH:23]=[CH:22][N:21]=1

参加物

5

反応物 2

HCID 25517Ammonium Chloride2 回HCID 71240769HCID 71240769、化合物2 回

生成物 1

HCID 866773074-methoxy-6-(1-methyl-3,6-dihydro-2H-pyridin-4-yl)-N'-(4-pyrazolo[1,5-a]pyridin-3-ylpyrimidin-2-yl)benzene-1,3-diamine収率 76.4%

試薬・触媒・溶媒 2

HCID 23925Iron触媒2 回HCID 962Water溶媒

実験手順

A mixture of N-[2-methoxy-4-(1-methyl-3,6-dihydro-2H-pyridin-4-yl)-5-nitrophenyl]-4-pyrazolo[1,5-a]pyridin-3-ylpyrimidin-2-amine (Intermediate 151, 285 mg, 0.56 mmol), iron (188 mg, 3.36 mmol), NH4Cl (21 mg, 0.39 mmol) ethanol (10.5 mL) and water (3.5 mL) was heated at reflux for 1.5 h. The reaction was judged to be incomplete so further NH4Cl (21 mg, 0.39 mmol) and iron (188 mg, 3.36 mmol) were added and the mixture was heated at reflux for a further 1.5 h. After cooling, the mixture was filtered and concentrated in vacuo. Purification by FCC, eluting with 2-10% 7N methanolic ammonia in CH2Cl2 gave the title compound (183 mg, 69%) as an orange gum which was used without further purification; 1H NMR: 2.30 (3H, s), 2.36-2.45 (2H, m), 2.60 (2H, t), 2.98-3.06 (2H, m), 3.74 (3H, s), 4.34 (2H, s), 5.73 (1H, s), 6.64 (1H, s), 7.09 (1H, m), 7.26 (1H, d), 7.38-7.49 (2H, m), 8.00 (1H, s), 8.35 (1H, d), 8.58 (1H, d), 8.80 (2H, m); m/z: ES+ MH+ 427.

後処理

  1. temperaturewas heated
  2. temperatureat reflux for 1.5 h
  3. additionwere added
  4. temperaturethe mixture was heated
  5. temperatureat reflux for a further 1.5 h
  6. temperatureAfter cooling
  7. filtrationthe mixture was filtered
  8. concentrationconcentrated in vacuo
  9. customPurification by FCC
  10. washeluting with 2-10% 7N methanolic ammonia in CH2Cl2

出典と根拠

ORDレコード
ord-a2fb77aa3d43496082f4b88e8cb14c63
出典データセット
uspto-grants-2015_02
特許番号
US08946235B2

反応ノート

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