Ethylene Glycol → 4-Hydroxycarbazole

HRID 1057650

反応式

HRID 1057650 の反応式
[CH2:1]1[C:13]2[NH:12][C:11]3[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=3)[C:5]=2[C:4](=[O:14])[CH2:3][CH2:2]1.C(O)CO.[Br-].[Li+].C(=O)([O-])[O-].[Li+].[Li+]>[Cu](Cl)Cl.O1CCOCC1>[CH:1]1[C:13]2[NH:12][C:11]3[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=3)[C:5]=2[C:4]([OH:14])=[CH:3][CH:2]=1

参加物

7

反応物 4

HCID 174Ethylene GlycolHCID 11125Lithium CarbonateHCID 82050Lithium BromideHCID 9291301,2,3,9-Tetrahydro-4H-carbazol-4-one

生成物 1

HCID 1042514-Hydroxycarbazole収率 18.5%

試薬・触媒・溶媒 2

HCID 24014Cupric Chloride触媒HCID 312751,4-Dioxane溶媒

反応条件

温度
120 °C

実験手順

To a mixture of 1,2,3,9-tetrahydro-4H-carbazol-4-one (6.02 g, 32.5 mmol) in 1:1 ethylene glycol: p-dioxane (100 mL) at 80° C. is added copper (II) chloride (21 g, 156.2 mmol). The mixture is heated for 20 minutes. The mixture is then partitioned between water and ethyl acetate. The layers are separated and the organic layer is washed three times with water (200 mL). The organic layer is dried over anhydrous sodium sulfate, filtered, and concentrated. The residue is dissolved in DMF (100 mL) to which is added lithium bromide (7.04 g, 81.25 mmol) and lithium carbonate (6.0 g, 81.25 mmol). The mixture is heated at 120° C. for 4.5 hours. The mixture is then partitioned between water and ether. The ether layer is washed three times with water (200 mL). The ether layer is dried over anhydrous sodium sulfate, filtered and concentrated. Column chromatography, silica gel (800 mL), using CH2Cl2 as eluent gave 1.1 g (18%) of the title compound; 1H NMR (CDCl3) δ5.26, 6.57, 7.01, 7.26, 7.41, 8.05, 8.26; Anal. Calcd for C12H9NO: C, 78.67; H, 4.95; N, 7.64. Found: C, 78.04; H, 4.94; N, 7.58.

後処理

  1. temperatureThe mixture is heated for 20 minutes
  2. customThe mixture is then partitioned between water and ethyl acetate
  3. customThe layers are separated
  4. washthe organic layer is washed three times with water (200 mL)
  5. dry with materialThe organic layer is dried over anhydrous sodium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated
  8. dissolutionThe residue is dissolved in DMF (100 mL) to which
  9. customThe mixture is then partitioned between water and ether
  10. washThe ether layer is washed three times with water (200 mL)
  11. dry with materialThe ether layer is dried over anhydrous sodium sulfate
  12. filtrationfiltered
  13. concentrationconcentrated

出典と根拠

ORDレコード
ord-c8e65610a98c4057991112db85ba2a4c
出典データセット
uspto-grants-2003_02
特許番号
US06514968B1

関連ノート

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