Lithium Carbonate → 9-Benzyl-6-methoxy-9H-carbazol-4-ol

HRID 1057655Notes

Reaction equation

HRID 1057655 reaction equation
[CH2:1]([N:8]1[C:20]2[CH2:19][CH2:18][CH2:17][C:16](=[O:21])[C:15]=2[C:14]2[C:9]1=[CH:10][CH:11]=[C:12]([O:22][CH3:23])[CH:13]=2)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.O1CCOCC1.[Br-].[Li+].C(=O)([O-])[O-].[Li+].[Li+]>C(O)CO.[Cu](Cl)Cl>[CH2:1]([N:8]1[C:20]2[CH:19]=[CH:18][CH:17]=[C:16]([OH:21])[C:15]=2[C:14]2[C:9]1=[CH:10][CH:11]=[C:12]([O:22][CH3:23])[CH:13]=2)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

7

Reactant 4

HCID 11125Lithium CarbonateHCID 312751,4-DioxaneHCID 82050Lithium BromideHCID 111095159-Benzyl-6-methoxy-1,2,3,9-tetrahydro-4H-carbazol-4-one

Product 1

HCID 97964539-Benzyl-6-methoxy-9H-carbazol-4-olYield 73%

Reagents, catalysts & solvents 2

HCID 24014Cupric ChlorideCatalystHCID 174Ethylene GlycolSolvent

Conditions

Temperature
80 °C

Procedure

To a mixture of 9-benzyl-6-methoxy-1,2,3,9-tetrahydro-4H-carbazol-4-one (4.23 g, 13.85 mmol) in ethylene glycol: p-dioxane ((1:1) 150 mL) is added copper (II) chloride (9.31 g, 69.26 mmol). The mixture is heated at 80° C. for 30 minutes. The mixture is partitioned between water and Et2O. The layers are separated and the organic layer washed with water (100 mL). The ether layer is dried over anhydrous sodium sulfate, filtered and concentrated. The residue is dissolved in DMF (50 mL) to which is added lithium bromide (2.45 g, 28.3 mmol) and lithium carbonate (2.09 g, 28.3 mnmol). The mixture is heated at 120° C. for 5 h. The mixture is partitioned between water and ethyl acetate. The layers are separated and the organic layer washed twice with water (200 mL). Column chromatography (250 mL) silica gel using ethyl acetate/ hexanes (20/80) gave 2.5 g (73%) of the title compound; IR (drift) 3471, 1482, 1469, 1450, 1328, 1198, 1171, 1144, 805, 799, 780, 745, 724, 717, 701 cm−1. 1H NMR (DMSO-d6) δ3.82, 5.54, 6.56, 6.97), 7.14, 7.23, 7.43, 7.72; Anal. Calcd for C20H17NO2: C, 79.18; H, 5.65; N, 4.62. Found: C, 78.99; H, 5.75; N, 4.63.

Workup

  1. customThe mixture is partitioned between water and Et2O
  2. customThe layers are separated
  3. washthe organic layer washed with water (100 mL)
  4. dry with materialThe ether layer is dried over anhydrous sodium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated
  7. dissolutionThe residue is dissolved in DMF (50 mL) to which
  8. temperatureThe mixture is heated at 120° C. for 5 h
  9. customThe mixture is partitioned between water and ethyl acetate
  10. customThe layers are separated
  11. washthe organic layer washed twice with water (200 mL)

Sources & evidence

ORD record
ord-ac4d131f7c31461d881ca44338bdbbf2
Source dataset
uspto-grants-2003_02
Patent number
US06514968B1

Reaction notes

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