Lithium Carbonate → HCID 18671690, compound

HRID 1057626Notes

Reaction equation

HRID 1057626 reaction equation
C1C=C[NH+]=CC=1.Br[Br-]Br.[Cl:10][C:11]1[CH:12]=[C:13]2[C:21](=[CH:22][CH:23]=1)[N:20]([CH2:24][C:25]1[CH:30]=[CH:29][C:28]([F:31])=[CH:27][CH:26]=1)[C:19]1[CH2:18][CH2:17][CH2:16][C:15](=[O:32])[C:14]2=1.[Br-].[Li+].C(=O)([O-])[O-].[Li+].[Li+]>C1COCC1.CN(C=O)C>[Cl:10][C:11]1[CH:12]=[C:13]2[C:21](=[CH:22][CH:23]=1)[N:20]([CH2:24][C:25]1[CH:30]=[CH:29][C:28]([F:31])=[CH:27][CH:26]=1)[C:19]1[CH:18]=[CH:17][CH:16]=[C:15]([OH:32])[C:14]2=1

Participants

6

Reactant 3

HCID 11125Lithium CarbonateHCID 82050Lithium BromideHCID 18671657HCID 18671657, compound

Product 1

HCID 18671690HCID 18671690, compoundYield 73%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolvent2×HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
75 °C

Procedure

Pyridinium bromide perbromide (0.6155 g, 0.0019 mol) is added to a solution of 6-chloro-9-(4-fluorobenzyl)-1,2,3,9-tetrahydro-4H-carbazol-4-one in THF (2.2 mL) and DMF (1.5 mL) and the mixture is heated to 75° C. After stirring for 3.5 h, the THF is removed under reduced pressure and the residue is partitioned between dichloromethane and brine. The combined organic layers are washed with dilute sodium thiosulfate/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 (0.3077 g, 0.0036 mol), lithium carbonate (0.2376 g, 0.0032 mol) and DMF (6 mL) is heated at 120° C. for two hours. The DMF is 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 dryness. The residue is chromatographed on silica gel (125 mL) using dichloromethane (100%) to give 0.3773 g (73%) of the title compound. An aliquot is recrystallized from dichloromethane/hexane; MS (ESI−) for C19H13ClFNO m/z 324.1 (M−H)−; IR (drift) 1510, 1468, 1444, 1335, 1297, 1263, 1232, 1218, 1147, 1116, 832, 822, 791, 778, 745 cm−1; 1H NMR (CDCl3) δ5.37, 5.43, 6.59, 6.94, 7.07, 7.23, 7.33, 8.31. Anal. Calcd for C19H13ClFNO: C, 70.05; H, 4.02; N, 4.30; Cl, 10.88. Found: C, 68.51; H, 3.96; N, 4.27.

Workup

  1. customthe THF is removed under reduced pressure
  2. customthe residue is partitioned between dichloromethane and brine
  3. washThe combined organic layers are washed with dilute sodium thiosulfate/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 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 dryness
  12. customThe residue is chromatographed on silica gel (125 mL)

Sources & evidence

ORD record
ord-31c9cb8ab19f4697881d910dfccfa1c2
Source dataset
uspto-grants-2003_02
Patent number
US06514968B1

Reaction notes

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