Ammonium Chloride → N4-(5-chloro-4-pyrazolo[1,5-a]pyridin-3-ylpyrimidin-2-yl)-5-methoxy-N1-methyl-N1-[2-(4-methylpiperazin-1-yl)ethyl]benzene-1,2,4-triamine

HRID 1842761ノート

反応式

HRID 1842761 の反応式
[Cl:1][C:2]1[C:3]([C:31]2[CH:32]=[N:33][N:34]3[CH:39]=[CH:38][CH:37]=[CH:36][C:35]=23)=[N:4][C:5]([NH:8][C:9]2[CH:14]=[C:13]([N+:15]([O-])=O)[C:12]([N:18]([CH3:28])[CH2:19][CH2:20][N:21]3[CH2:26][CH2:25][N:24]([CH3:27])[CH2:23][CH2:22]3)=[CH:11][C:10]=2[O:29][CH3:30])=[N:6][CH:7]=1.[NH4+].[Cl-]>CCO.O.[Fe]>[Cl:1][C:2]1[C:3]([C:31]2[CH:32]=[N:33][N:34]3[CH:39]=[CH:38][CH:37]=[CH:36][C:35]=23)=[N:4][C:5]([NH:8][C:9]2[CH:14]=[C:13]([NH2:15])[C:12]([N:18]([CH3:28])[CH2:19][CH2:20][N:21]3[CH2:26][CH2:25][N:24]([CH3:27])[CH2:23][CH2:22]3)=[CH:11][C:10]=2[O:29][CH3:30])=[N:6][CH:7]=1

参加物

6

反応物 2

HCID 25517Ammonium ChlorideHCID 71240746N-(5-chloro-4-pyrazolo[1,5-a]pyridin-3-ylpyrimidin-2-yl)-2-methoxy-N'-methyl-N'-(2-(4-methylpiperazin-1-yl)ethyl]-5-nitrobenzene-1,4-diamine

生成物 1

HCID 86677275N4-(5-chloro-4-pyrazolo[1,5-a]pyridin-3-ylpyrimidin-2-yl)-5-methoxy-N1-methyl-N1-[2-(4-methylpiperazin-1-yl)ethyl]benzene-1,2,4-triamine収率 94%

試薬・触媒・溶媒 3

HCID 23925Iron触媒HCID 702Ethanol溶媒HCID 962Water溶媒

実験手順

A mixture of N-(5-chloro-4-pyrazolo[1,5-a]pyridin-3-ylpyrimidin-2-yl)-2-methoxy-N′-methyl-N′-[2-(4-methylpiperazin-1-yl)ethyl]-5-nitrobenzene-1,4-diamine (0.182 g, 0.33 mmol), iron (0.110 g, 1.98 mmol) and NH4Cl (0.012 g, 0.23 mmol) in EtOH (10 mL) and water (3.33 mL) was heated at reflux for 1.5 h. The mixture was then cooled to r.t., filtered and concentrated in vacuo. Purification by ion exchange chromatography, using an SCX column and eluting with 1M methanolic ammonia provided a brown gum (162 mg) after concentration of appropriate fractions. Further purification by FCC, eluting with 2-7% 1M methanolic ammonia in CH2Cl2 gave the title compound (0.148 g, 86%) as a yellow gum; 1H NMR: (CDCl3) 2.28 (3H, s), 2.32-2.63 (10H, m), 2.70 (3H, s), 2.98 (2H, t), 3.84 (3H, s), 4.05 (2H, d), 6.71 (1H, s), 6.95 (1H, td), 7.38 (1H, ddd), 7.52 (1H, d), 7.88 (1H, s), 8.36 (1H, s), 8.57 (1H, d), 8.65 (1H, d), 8.93 (1H, s); m/z: ES+ MH+ 522.57.

後処理

  1. temperaturewas heated
  2. temperatureat reflux for 1.5 h
  3. filtrationfiltered
  4. concentrationconcentrated in vacuo
  5. customPurification by ion exchange chromatography
  6. washeluting with 1M methanolic ammonia

出典と根拠

ORDレコード
ord-77a3ae171f75453eb2ee37c6fe255593
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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