tert-Butanol → HCID 67357244、化合物

HRID 1478906ノート

反応式

HRID 1478906 の反応式
C1(P(N=[N+]=[N-])(C2C=CC=CC=2)=[O:8])C=CC=CC=1.CC[N:20]([CH2:23]C)CC.[Br:25][C:26]1[C:30]2[CH:31]=[N:32][C:33](C(O)=O)=[CH:34][C:29]=2[N:28]([CH2:38][CH3:39])[CH:27]=1.[CH3:40][C:41]([OH:44])([CH3:43])[CH3:42]>CN(C=O)C>[Br:25][C:26]1[C:30]2[CH:31]=[N:32][C:33]([NH:20][C:23](=[O:8])[O:44][C:41]([CH3:43])([CH3:42])[CH3:40])=[CH:34][C:29]=2[N:28]([CH2:38][CH3:39])[CH:27]=1

参加物

6

反応物 4

HCID 6386tert-ButanolHCID 8471TriethylamineHCID 199401P,P-Diphenylphosphinic azideHCID 71087282HCID 71087282、化合物

生成物 1

HCID 67357244HCID 67357244、化合物収率 9.9%

試薬・触媒・溶媒 1

HCID 6228Dimethylformamide溶媒

反応条件

温度
0 °C

実験手順

A mixture of diphenylphosphoryl azide (4.3 g, 16 mmol), Et3N (7.3 ml, 52 mmol) and 3-bromo-1-ethyl-1H-pyrrolo[3,2-c]pyridine-6-carboxylic acid (3B, 2.8 g, 10 mmol) in DMF (30 ml) was stirred at 0° C. for 1 h. The mixture was extracted with EtOAc/H2O. The organic layer was washed with brine, dried over MgSO4 and concentrated in vacuo. The crude mixture was dissolved in toluene (30 ml) and added 2-methylpropan-2-ol (3.9 g, 52 mmol). The mixture was stirred at 70° C. for 2 h. The mixture was concentrated in vacuo and purified by chromatography (SiO2, hexanes:EtOAc=1:1) to give tert-butyl 3-bromo-1-ethyl-1H-pyrrolo[3,2-c]pyridin-6-ylcarbamate (3C, 340 mg, 0.99 mmol, 9.5% yield) as a white powder. 1H NMR (400 MHz, DMSO-d6) δ ppm 1.35 (t, J=7.20 Hz, 3 H) 1.49 (s, 9 H) 4.14 (q, J=7.33 Hz, 2 H) 7.60 (s, 1 H) 7.83 (d, J=0.76 Hz, 1 H) 8.36 (d, J=0.76 Hz, 1 H) 9.59 (s, 1 H).

後処理

  1. extractionThe mixture was extracted with EtOAc/H2O
  2. washThe organic layer was washed with brine
  3. dry with materialdried over MgSO4
  4. concentrationconcentrated in vacuo
  5. dissolutionThe crude mixture was dissolved in toluene (30 ml)
  6. stirringThe mixture was stirred at 70° C. for 2 h
  7. concentrationThe mixture was concentrated in vacuo
  8. custompurified by chromatography (SiO2, hexanes:EtOAc=1:1)

出典と根拠

ORDレコード
ord-e2d51442651945d2b9715b14c09d1839
出典データセット
uspto-grants-2016_08
特許番号
US09403819B2

反応ノート

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