Lithium Carbonate → HCID 18671697, compound

HRID 1057610Notes

Reaction equation

HRID 1057610 reaction equation
C1C=C[NH+]=CC=1.Br[Br-]Br.[CH2:10]([N:17]1[C:29]2[CH2:28][CH2:27][CH2:26][C:25](=[O:30])[C:24]=2[C:23]2[C:18]1=[C:19]([F:31])[CH:20]=[CH:21][CH:22]=2)[C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1.[Br-].[Li+].C(=O)([O-])[O-].[Li+].[Li+]>C1COCC1.CN(C=O)C>[CH2:10]([N:17]1[C:29]2[CH:28]=[CH:27][CH:26]=[C:25]([OH:30])[C:24]=2[C:23]2[C:18]1=[C:19]([F:31])[CH:20]=[CH:21][CH:22]=2)[C:11]1[CH:12]=[CH:13][CH:14]=[CH:15][CH:16]=1

Participants

6

Reactant 3

HCID 11125Lithium CarbonateHCID 82050Lithium BromideHCID 18671682HCID 18671682, compound

Product 1

HCID 18671697HCID 18671697, compoundYield 52%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolvent2×HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
75 °C

Procedure

Pyridinium bromide perbromide (2.9945 g, 0.0094 mol) is added to a mixture of 9-benzyl-8-fluoro-1,2,3,9-tetrahydro-4H-carbazol-4-one (2.1145 g, 0.0072 mol) in THF (22 mL) and DMF (16 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 ethyl acetate and brine. The combined organic layers are washed with dilute sodium thiosulfate/brine and the aqueous layer is backwashed with ethyl acetate. The combined organic layers are dried over magnesium sulfate and concentrated under reduced pressure to give a residue. The residue is recrystallized from ethyl acetate/heptane and the resulting solids are combined with lithium bromide (1.1338 g, 0.013 mol), lithium carbonate (0.8831 g, 0.012 mol), and DMF (24 mL) and heated to 120° C. After 1.5 h, the mixture is partitioned between ethyl acetate and brine. The combined organic layers are washed with dilute brine and then dried over sodium sulfate and concentrated to an oil. The oil is chromatographed on silica gel (150 mL) using dichloromethane (100) to give 1.0857 g (52%) of the title compound; mp 155-156° C.; MS (ESI−) for C19H14FNO m/z 290.1 (M−H)−; IR (drift) 3524, 1581, 1498, 1456, 1432, 1343, 1318, 1272, 1239, 1134, 966, 790, 731, 714, 698 cm−1; 1H NMR (CDCl3) δ5.33, 5.69, 6.59, 6.98, 7.14, 7.25, 8.10. Anal. Calcd for C19H14FNO: C, 78.33; H, 4.84; N, 4.81. Found: C, 77.67; H, 4.90; N, 4.71.

Workup

  1. customTHF is removed under reduced pressure
  2. customthe residue is partitioned between ethyl acetate 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. customThe residue is recrystallized from ethyl acetate/heptane
  8. temperatureheated to 120° C
  9. waitAfter 1.5 h
  10. customthe mixture is partitioned between ethyl acetate and brine
  11. washThe combined organic layers are washed with dilute brine
  12. dry with materialdried over sodium sulfate
  13. concentrationconcentrated to an oil
  14. customThe oil is chromatographed on silica gel (150 mL)

Sources & evidence

ORD record
ord-a15abd2a5823416d86650ea97084f1f3
Source dataset
uspto-grants-2003_02
Patent number
US06514968B1

Reaction notes

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