Lithium Carbonate → HCID 18671681, compound

HRID 1057641Notes

Reaction equation

HRID 1057641 reaction equation
C1C=C[NH+]=CC=1.Br[Br-]Br.[F:10][C:11]1[CH:32]=[CH:31][C:14]([CH2:15][N:16]2[C:28]3[CH2:27][CH2:26][CH2:25][C:24](=[O:29])[C:23]=3[C:22]3[C:17]2=[CH:18][CH:19]=[C:20]([CH3:30])[CH:21]=3)=[CH:13][CH:12]=1.[Br-].[Li+].C(=O)([O-])[O-].[Li+].[Li+]>C1COCC1.CN(C=O)C>[F:10][C:11]1[CH:32]=[CH:31][C:14]([CH2:15][N:16]2[C:28]3[CH:27]=[CH:26][CH:25]=[C:24]([OH:29])[C:23]=3[C:22]3[C:17]2=[CH:18][CH:19]=[C:20]([CH3:30])[CH:21]=3)=[CH:13][CH:12]=1

Participants

6

Reactant 3

HCID 11125Lithium CarbonateHCID 82050Lithium BromideHCID 18671683HCID 18671683, compound

Product 1

HCID 18671681HCID 18671681, compoundYield 8%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolvent2×HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
75 °C

Procedure

Pyridinium bromide perbromide (0.8153 g, 0.0026 mol) is added to a mixture of 9-(4-fluorobenzyl)-6-methyl-1,2,3,9-tetrahydro-4H-carbazol-4-one (0.6351 g, 0.0021 mol) in dry THF (4.2 mL) and dry DMF (3 mL) and the mixture is heated to 75° C. After stirring for 6 h, additional pyridinium bromide perbromide (0.0951 g, 0.30 mmol) is added and the mixture is stirred another hour. After storing in the freezer overnight, the mixture is again heated for another 40 min. 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 to dryness. The residue is combined with lithium bromide (0.4092 g, 0.0047 mol), lithium carbonate (0.3652 g, 0.0049 mol) and dry DMF (12 mL) and heated at 120° C. for 1.5 h. DMF is removed under high vacuum and the mixture 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 (100 mL) using hexane (100%, to remove oil from sample) followed by ethyl acetate (100%). The residue is chromatographed again on silica gel (125 mL) using ethyl acetate/heptane (10/90) to give 0.0505 g (8%) of the title compound; MS (ESI−) for C20H16FNO m/z 304.1 (M−H)−; 1H NMR (CDCl3) δ2.54, 5.33, 5.43, 6.57, 6.93, 7.08, 7.24, 8.12.

Workup

  1. stirringthe mixture is stirred another hour
  2. customAfter storing in the freezer overnight
  3. temperaturethe mixture is again heated for another 40 min
  4. customTHF is removed under reduced pressure
  5. customthe residue is partitioned between dichloromethane and brine
  6. washThe combined organic layers are washed with dilute sodium thiosulfate/brine
  7. dry with materialThe combined organic layers are dried over magnesium sulfate
  8. concentrationconcentrated to dryness
  9. temperatureheated at 120° C. for 1.5 h
  10. customDMF is removed under high vacuum
  11. customthe mixture is partitioned between dichloromethane and water
  12. dry with materialThe combined organic layers are dried over sodium sulfate
  13. concentrationconcentrated to dryness
  14. customThe residue is chromatographed on silica gel (100 mL)
  15. customThe residue is chromatographed again on silica gel (125 mL)

Sources & evidence

ORD record
ord-5bdd92f457ae4636b1ce57d5fa417276
Source dataset
uspto-grants-2003_02
Patent number
US06514968B1

Reaction notes

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