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1,2-Dichloroethane → Methyl 1-methyl-4-(1-methyl-4-(1-methyl-4-(1-methyl-4-nitro-1H-pyrrole-2-carboxamido)-1H-pyrrole-2-carboxamido)-1H-pyrrole-2-carboxamido)-1H-pyrrole-2-carboxylate

HRID 1776671
ノート
印刷プレビュー

反応式

HRID 1776671 の反応式
[CH3:1][N:2]1[CH:6]=[C:5]([NH:7][C:8]([C:10]2[N:11]([CH3:18])[CH:12]=[C:13]([N+:15]([O-])=O)[CH:14]=2)=[O:9])[CH:4]=[C:3]1[C:19]([O:21][CH3:22])=[O:20].Cl.[H][H].[CH3:26][N:27]1[CH:31]=[C:30]([NH:32][C:33]([C:35]2[N:36]([CH3:43])[CH:37]=[C:38]([N+:40]([O-:42])=[O:41])[CH:39]=2)=[O:34])[CH:29]=[C:28]1[C:44]([OH:46])=O.C(Cl)CCl.CCN(C(C)C)C(C)C>[Pd].CC(N(C)C)=O>[CH3:1][N:2]1[CH:6]=[C:5]([NH:7][C:8]([C:10]2[N:11]([CH3:18])[CH:12]=[C:13]([NH:15][C:44]([C:28]3[N:27]([CH3:26])[CH:31]=[C:30]([NH:32][C:33]([C:35]4[N:36]([CH3:43])[CH:37]=[C:38]([N+:40]([O-:42])=[O:41])[CH:39]=4)=[O:34])[CH:29]=3)=[O:46])[CH:14]=2)=[O:9])[CH:4]=[C:3]1[C:19]([O:21][CH3:22])=[O:20]
参加物実験手順後処理出典と根拠反応ノート

参加物

9

反応物 6

HCID 111,2-DichloroethaneHCID 313Hydrochloric AcidHCID 81531DiisopropylethylamineHCID 4041101-Methyl-4-(1-methyl-4-nitropyrrole-2-carboxamido)pyrrole-2-carboxylic acidHCID 592893Methyl 1-methyl-4-(1-methyl-4-nitropyrrole-2-carboxamido)pyrrole-2-carboxylateHCID 178418361HCID 178418361、化合物

生成物 1

HCID 59440204Methyl 1-methyl-4-(1-methyl-4-(1-methyl-4-(1-methyl-4-nitro-1H-pyrrole-2-carboxamido)-1H-pyrrole-2-carboxamido)-1H-pyrrole-2-carboxamido)-1H-pyrrole-2-carboxylate収率 76%

試薬・触媒・溶媒 2

HCID 23938Palladium触媒HCID 31374Dimethylacetamide溶媒2 回

実験手順

In a hydrogenation bottle was added methyl 1-methyl-4-(1-methyl-4-nitro-1H-pyrrole-2-carboxamido)-1H-pyrrole-2-carboxylate (2.0 g, 6.53 mmol), 80 ml of DMA, 500 mg of 10% Pd/C (50% wet) and 0.4 ml of HCl (conc.). After evacuation under vacuum, the bottle was placed under 50 psi hydrogen and shaken for 4 hours. The mixture was filtered through celite, evaporated to dryness without further purification. To the dry mixture was added 1-methyl-4-(1-methyl-4-nitro-1H-pyrrole-2-carboxamido)-1H-pyrrole-2-carboxylic acid (1.49 g, 5.10 mmol), 30 ml of DMA, EDC (4.0 g, 20.8 mmol) and DIPEA (1.0 ml, 5.75 mmol). The mixture was stirred under Ar overnight, concentrated, diluted with Hexane/EtAc (1:1, 10 ml) and water 10 ml to form precipitates. The precipitates were filtered, washed 1M NaH2PO4, 1 M NaHCO3 and water, dried over P2O5 under vacuum to afford 2.13 g (76%) of the title product. 1H NMR (DMSO) 10.28 (s, 1H), 10.25 (s, 1H), 9.78 (s, 1H), 8.18 (s, 1H), 7.86 (s, 1H), 7.52 (s, 1H), 7.31 (d, 1H, J=1.7 Hz), 7.25 (s, 1H), 7.23 (s, 1H), 7.17 (d, 1H, J=1.5 Hz), 6.98 (s, 1H), 6.71 (s, 1H), 4.02 (s, 3H), 3.94 (s, 3H), 3.83 (s, 3H), 3.73 (s, 3H), 3.56 (s, 3H), 1.47 (s, 9H); 13C NMR 160.78, 158.93, 158.06, 157.81, 135.25, 127.28, 126.36, 123.78, 122.57, 121.91, 121.40, 120.94, 119.65, 110.73, 108.39, 107.34, 103.75, 80.81, 51.57, 39.74, 38.52, 38.22, 37.08, 28.63; MS m/z+573.2 (M+Na).

後処理

  1. filtrationThe mixture was filtered through celite
  2. customevaporated to dryness without further purification
  3. stirringThe mixture was stirred under Ar overnight
  4. concentrationconcentrated
  5. additiondiluted with Hexane/EtAc (1:1, 10 ml) and water 10 ml
  6. customto form
  7. customprecipitates
  8. filtrationThe precipitates were filtered
  9. washwashed 1M NaH2PO4, 1 M NaHCO3 and water
  10. dry with materialdried over P2O5 under vacuum

出典と根拠

ORDレコード
ord-37be948e9c9642beb4c7fadb5cbf9680
出典データセット
uspto-grants-2016_02
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US09265841B2

反応ノート

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