Triethylamine → Tert-butyl 3-((2-bromo-5-nitropyridin-4-yl)amino)piperidine-1-carboxylate

HRID 919643ノート

反応式

HRID 919643 の反応式
[NH2:1][CH:2]1[CH2:7][CH2:6][CH2:5][N:4]([C:8]([O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:9])[CH2:3]1.[Br:15][C:16]1[CH:21]=[C:20](Br)[C:19]([N+:23]([O-:25])=[O:24])=[CH:18][N:17]=1.CCN(CC)CC.[OH-].[Na+]>CCO.CCOC(C)=O>[Br:15][C:16]1[CH:21]=[C:20]([NH:1][CH:2]2[CH2:7][CH2:6][CH2:5][N:4]([C:8]([O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:9])[CH2:3]2)[C:19]([N+:23]([O-:25])=[O:24])=[CH:18][N:17]=1

参加物

7

反応物 4

HCID 8471TriethylamineHCID 14798Sodium HydroxideHCID 5458091-BOC-3-AminopiperidineHCID 160998502,4-Dibromo-5-nitropyridine

生成物 1

HCID 86706484Tert-butyl 3-((2-bromo-5-nitropyridin-4-yl)amino)piperidine-1-carboxylate収率 43.3%

試薬・触媒・溶媒 2

HCID 702Ethanol溶媒HCID 8857Ethyl Acetate溶媒

実験手順

The tert-butyl 3-aminopiperidine-1-carboxylate (1.43 g, 7.14 mmol, 1.0 eq) was added dropwise to a solution of 2,4-dibromo-5-nitropyridine (2 g, 7.14 mmol, 1.0 eq) and Et3N (0.73 g, 7.14 mmol, 1.0 eq) in EtOH (20 mL) at reflux temperature. The reaction mixture was heated at refluxing for 16 h and then the solvent was concentrated in vacuo to afford a residue. The residue was treated with 1 N NaOH solution and extraction with EtOAc. The organic phase was separated, dried (Na2SO4) and concentration in vacuo to afford an residue which was purified by silica gel column chromatography with EtOAc in PE (⅕ v/v) to give the title compound (1.24 g, 42%) as yellow solid. 1H NMR (400 MHz, CDCl3) δ: 8.99 (s, 1H), 8.25 (s, 1H), 6.98 (s, 1H), 3.81-3.79 (m, 1H), 3.61-3.60 (m, 2H), 3.37-3.35 (m, 2H), 2.02 (m, 1H), 1.86-1.77 (m, 3H), 1.47 (s, 9H). ESI-MS (M+H+): 401.0.

後処理

  1. temperatureat reflux temperature
  2. temperatureThe reaction mixture was heated
  3. temperatureat refluxing for 16 h
  4. concentrationthe solvent was concentrated in vacuo
  5. customto afford a residue
  6. customThe organic phase was separated
  7. customdried
  8. concentration(Na2SO4) and concentration in vacuo
  9. customto afford an residue which
  10. customwas purified by silica gel column chromatography with EtOAc in PE (⅕ v/v)

出典と根拠

ORDレコード
ord-4890278b8bc34944a8e2ba54c2ce8c3e
出典データセット
uspto-grants-2016_03
特許番号
US09273028B2

反応ノート

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