Lithium Carbonate → 9-Benzyl-7-methoxy-9H-carbazol-4-ol

HRID 1057660Notes

Reaction equation

HRID 1057660 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][C:11]([O:22][CH3:23])=[CH:12][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+]>[Cu](Cl)Cl.C(O)CO>[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][C:11]([O:22][CH3:23])=[CH:12][CH:13]=2)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

7

Reactant 4

HCID 11125Lithium CarbonateHCID 312751,4-DioxaneHCID 82050Lithium BromideHCID 11023142HCID 11023142, compound

Product 1

HCID 186716949-Benzyl-7-methoxy-9H-carbazol-4-olYield 61%

Reagents, catalysts & solvents 2

HCID 24014Cupric ChlorideCatalystHCID 174Ethylene GlycolSolvent

Conditions

Temperature
120 °C

Procedure

To a mixture of 9-benzyl-7-methoxy-1,2,3,9-tetrahydro-4H-carbazol-4-one (1.65 g, 5.4 mmol) in 1:1 p-dioxane:ethylene glycol (50 mL) at 80° C. is added copper (II) chloride (3.6 g, 27 mmol). The mixture is heated for 17 minutes. The mixture is partitioned between water and ethyl acetate. The layers are separated and the ethyl acetate layer washed twice with water (200 mL). The ethyl acetate is dried over anhydrous sodium sulfate, filtered, and concentrated. The residue is dissolved in DMF (50 mL). Lithium bromide (0.94 g, 10.8 mmol) and lithium carbonate (0.8 g, 10.8 mmol) is added and the mixture heated to 120° C. for 6 hours. The mixture is partitioned between water and ethyl acetate. The layers are separated and the ethyl acetate layer washed twice with water (200 mL). The ethyl acetate is dried over anhydrous sodium sulfate, filtered and concentrated. Column chromatography, silica gel (100 mL), using CH2Cl2/CH3OH (96/4) gave 1.0 gm (61%) of the title compound; IR (drift) 1607, 1465, 1334, 1330, 1320, 1276, 1251, 1207, 1102, 809, 745, 740, 722, 711, 696 cm−1. 1H NMR (CDCl3) δ3.9, 5.4, 6.6, 6.8, 6.9, 7.2, 7.2, 8.2); Anal. Calcd for C20H17NO2: C, 79.18; H, 5.65; N, 4.62. Found: C, 78.35; H, 5.66; N, 4.55.

Workup

  1. temperatureThe mixture is heated for 17 minutes
  2. customThe mixture is partitioned between water and ethyl acetate
  3. customThe layers are separated
  4. washthe ethyl acetate layer washed twice with water (200 mL)
  5. dry with materialThe ethyl acetate is dried over anhydrous sodium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated
  8. dissolutionThe residue is dissolved in DMF (50 mL)
  9. customThe mixture is partitioned between water and ethyl acetate
  10. customThe layers are separated
  11. washthe ethyl acetate layer washed twice with water (200 mL)
  12. dry with materialThe ethyl acetate is dried over anhydrous sodium sulfate
  13. filtrationfiltered
  14. concentrationconcentrated

Sources & evidence

ORD record
ord-e2fa644a5e114bb9a960ecbef4a3a315
Source dataset
uspto-grants-2003_02
Patent number
US06514968B1

Reaction notes

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