Lithium Carbonate → HCID 12967330, compound

HRID 1057599Notes

Reaction equation

HRID 1057599 reaction equation
C1C=C[NH+]=CC=1.Br[Br-]Br.[Cl:10][C:11]1[CH:12]=[CH:13][CH:14]=[C:15]2[C:23]=1[N:22]([CH2:24][C:25]1[CH:30]=[CH:29][C:28]([F:31])=[CH:27][CH:26]=1)[C:21]1[CH2:20][CH2:19][CH2:18][C:17](=[O:32])[C:16]2=1.[Br-].[Li+].C(=O)([O-])[O-].[Li+].[Li+]>C1COCC1.CN(C=O)C>[Cl:10][C:11]1[CH:12]=[CH:13][CH:14]=[C:15]2[C:23]=1[N:22]([CH2:24][C:25]1[CH:30]=[CH:29][C:28]([F:31])=[CH:27][CH:26]=1)[C:21]1[CH:20]=[CH:19][CH:18]=[C:17]([OH:32])[C:16]2=1

Participants

6

Reactant 3

HCID 11125Lithium CarbonateHCID 82050Lithium BromideHCID 18671659HCID 18671659, compound

Product 1

HCID 12967330HCID 12967330, compoundYield 72%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolvent2×HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
75 °C

Procedure

Pyridinium bromide perbromide (0.1988 g, 0.62 mmol) is added to a solution of 8-chloro-9-(4-fluorobenzyl)-1,2,3,9-tetrahydro-4H-carbazol-4-one in THF (0.7 mL) and DMF (0.5 mL) and the mixture is heated to 75° C. After stirring for 5.5 h, THF is removed under reduced pressure and the residue is partitioned between dichloromethane and brine. The combined organic layers are washed with dilute sodium sulfate/brine and the aqueous layer is backwashed with dichloromethane. The combined organic layers are dried over magnesium sulfate and concentrated under reduced pressure to give a residue. A mixture of the resulting residue, lithium bromide (0.0976 g, 0.0011 mol), lithium carbonate (0.0762 g, 0.0010 mol) and DMF (2 mL) is heated at 120° C. for two hours. The DMF is then removed under high vacuum and the residue is partitioned between dichloromethane and water. The combined organic layers are dried over sodium sulfate and concentrated to an oil. The oil is chromatographed on silica gel (80 mL) using 15% ethyl acetate in heptane/dichloromethane (6:1) to give 0.1199 g (72%) of the title compound; mp 142-145° C.; MS (ESI−) for C19H13ClFNO m/z 324.1 (M−H)−; IR (drift) 3521, 1591, 1508, 1457, 1416, 1351, 1337, 1311, 1269, 1226, 1218, 1110, 852, 791, 736 cm−1; 1H NMR (CDCl3) δ5.38, 5.94, 6.60, 6.93, 7.06, 7.18, 7.26, 7.36, 8.29. Anal. Calcd for C19H13ClFNO: C, 70.05; H, 4.02; N, 4.30. Found: C, 69.26; H, 4.05; N, 4.20.

Workup

  1. customTHF is removed under reduced pressure
  2. customthe residue is partitioned between dichloromethane and brine
  3. washThe combined organic layers are washed with dilute sodium sulfate/brine
  4. dry with materialThe combined organic layers are dried over magnesium sulfate
  5. concentrationconcentrated under reduced pressure
  6. customto give a residue
  7. temperatureis heated at 120° C. for two hours
  8. customThe DMF is then removed under high vacuum
  9. customthe residue is partitioned between dichloromethane and water
  10. dry with materialThe combined organic layers are dried over sodium sulfate
  11. concentrationconcentrated to an oil
  12. customThe oil is chromatographed on silica gel (80 mL)

Sources & evidence

ORD record
ord-c8b33addabe14f24a6521b8be4b02f0e
Source dataset
uspto-grants-2003_02
Patent number
US06514968B1

Reaction notes

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