Lithium Carbonate → HCID 18671696, compound

HRID 1057629Notes

Reaction equation

HRID 1057629 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=[CH:19][CH:20]=[C:21]([F:31])[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=[CH:19][CH:20]=[C:21]([F:31])[CH:22]=2)[C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1

Participants

6

Reactant 3

HCID 11125Lithium CarbonateHCID 82050Lithium BromideHCID 186716779-Benzyl-6-fluoro-1,2,3,9-tetrahydro-4H-carbazol-4-one

Product 1

HCID 18671696HCID 18671696, compoundYield 59.1%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolvent2×HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
75 °C

Procedure

Pyridinium bromide perbromide (0.4620 g, 0.0014 mol) is added to a mixture of 9-benzyl-6-fluoro-1,2,3,9-tetrahydro-4H-carbazol-4-one (0.3271 g, 0.0011 mol) in THF (3.4 mL) and DMF (2.4 mL) and the mixture is heated to 75° C. After stirring for 6.5 h, the mixture is stored in the freezer overnight. Heating is resumed for an additional 2.5 h, at which time 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 sodium sulfate and concentrated under reduced pressure to give a residue. The residue is heated to 120° C. in DMF (5 mL) with lithium bromide (0.2348 g, 0.0027 mol) and lithium carbonate (0.1813 g, 0.0025 mol). After 2 h, DMF is removed under high vacuum and the mixture is partitioned between dichloromethane and water. The combined organic layers are washed with water and the aqueous layer is backwashed with dichloromethane. The combined organic layers are dried over sodium sulfate and concentrated to an oil. The oil is chromatographed on silica gel (100 mL) using dichloromethane/hexane (30/70 and 50/50) to give 0.1893 g (58%) of the title compound. An aliquot is precipitated from hexane/ ether; MS (ESI+) for C19H14FNO m/z 292.2 (M+H)+; IR (drift) 1483, 1466, 1451, 1337, 1304, 1174, 1157, 1138, 884, 859, 794, 777, 745, 713, 700 cm−1; 1H NMR (CDCl3) δ5.34, 5.47, 6.56, 6.95, 7.13, 7.20-7.30, 8.01. Anal. Calcd for C19H14FNO: C, 78.33; H, 4.84; N, 4.81. Found: C, 78.17; H, 4.83; N, 4.78.

Workup

  1. customis stored in the freezer overnight
  2. temperatureHeating
  3. customis removed under reduced pressure
  4. customthe residue is partitioned between dichloromethane and brine
  5. washThe combined organic layers are washed with dilute sodium thiosulfate/brine
  6. dry with materialThe combined organic layers are dried over sodium sulfate
  7. concentrationconcentrated under reduced pressure
  8. customto give a residue
  9. waitAfter 2 h
  10. customDMF is removed under high vacuum
  11. customthe mixture is partitioned between dichloromethane and water
  12. washThe combined organic layers are washed with water
  13. dry with materialThe combined organic layers are dried over sodium sulfate
  14. concentrationconcentrated to an oil
  15. customThe oil is chromatographed on silica gel (100 mL)

Sources & evidence

ORD record
ord-fa00e732eee341e0992ef1f429619a2a
Source dataset
uspto-grants-2003_02
Patent number
US06514968B1

Reaction notes

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