Sodium Carbonate → 4-(5-methylthiophen-2-yl)-1-trityl-1H-imidazole

HRID 1429110ノート

反応式

HRID 1429110 の反応式
IC1[N:3]=[CH:4][N:5]([C:7]([C:20]2[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=2)([C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)[C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)[CH:6]=1.[CH3:26][C:27]1[S:31][C:30](B2OC(C)(C)C(C)(C)O2)=[CH:29][CH:28]=1.[C:41]([O-])([O-])=O.[Na+].[Na+]>O.O1CCOCC1>[CH3:41][C:30]1[S:31][C:27]([C:26]2[N:3]=[CH:4][N:5]([C:7]([C:14]3[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=3)([C:8]3[CH:9]=[CH:10][CH:11]=[CH:12][CH:13]=3)[C:20]3[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=3)[CH:6]=2)=[CH:28][CH:29]=1

参加物

6

反応物 3

HCID 10340Sodium CarbonateHCID 6182524-Iodo-1-tritylimidazoleHCID 118169404,4,5,5-Tetramethyl-2-(5-methylthiophen-2-yl)-1,3,2-dioxaborolane

生成物 1

HCID 675105464-(5-methylthiophen-2-yl)-1-trityl-1H-imidazole収率 83.1%

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 312751,4-Dioxane溶媒

実験手順

A mixture of 4-iodo-1-trityl-1H-imidazole (7.95 g, 18.2 mmol), 5-methylthiophene-2-boronic acid pinacol ester (4.90 g, 21.9 mmol), Na2CO3 (7.66 g, 73.0 mmol) in H2O (20 mL) and dioxane (100 mL) was degassed (N2 bubbling). Pd(PPh3)4 (500 mg) was added and the mixture was heated to reflux for 4 h. The mixture was allowed to cool to room temperature and concentrated. The mixture was diluted with CH2Cl2 and H2O and the organic phase was separated. The aqueous phase was re-extracted (CH2Cl2) and the combined organics were washed (saturated aqueous NaCl), dried (MgSO4), filtered and concentrated to give a solid residue. The residue was purified by flash chromatography (EtOAc/CH2Cl2/hexanes 4:50:50 then 6:50:50 then 8:50:50) to give 4-(5-methylthiophen-2-yl)-1-trityl-1H-imidazole (6.15 g, 83%) as a colourless solid. 1H NMR (CDCl3, 400 MHz) δ2.46 (d, J=0.9 Hz, 3H), 6.62-6.65 (m, 1H), 6.94 (d, J=1.4 Hz, 1H), 6.99 (d, J=3.5 Hz, 1H), 7.15-7.21 (m, 6H), 7.31-7.37 (m, 9H), 7.41 (d, J=1.4 Hz, 1H); 13C NMR (CDCl3, 100 MHz) δ15.3, 75.5, 116.1, 121.7, 125.5, 128.1, 128.1, 129.8, 135.6, 136.4, 137.8, 138.9, 142.2; HRMS (EI) m/z 406.1496 C27H22N2S [M]+. requires 406.1498.

後処理

  1. customwas degassed (N2 bubbling)
  2. additionPd(PPh3)4 (500 mg) was added
  3. temperaturethe mixture was heated
  4. temperatureto reflux for 4 h
  5. concentrationconcentrated
  6. additionThe mixture was diluted with CH2Cl2 and H2O
  7. customthe organic phase was separated
  8. extractionThe aqueous phase was re-extracted (CH2Cl2)
  9. washthe combined organics were washed (saturated aqueous NaCl)
  10. dry with materialdried (MgSO4)
  11. filtrationfiltered
  12. concentrationconcentrated
  13. customto give a solid residue
  14. customThe residue was purified by flash chromatography (EtOAc/CH2Cl2/hexanes 4:50:50

出典と根拠

ORDレコード
ord-7a3c942d60354a5687413c14726e0f58
出典データセット
uspto-grants-2015_01
特許番号
US08937303B2

反応ノート

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