Lithium Carbonate → HCID 18671685, compound

HRID 1057623Notes

Reaction equation

HRID 1057623 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]([Cl: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]([Cl: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 18671670HCID 18671670, compound

Product 1

HCID 18671685HCID 18671685, compoundYield 72.9%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolvent2×HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
75 °C

Procedure

Pyridinium bromide perbromide (0.5495 g, 0.0017 mol) is added to a solution of 9-benzyl-6-chloro-1,2,3,9-tetrahydro-4H-carbazol-4-one (0.4406 g, 0.0014 mol) in THF (2.8 mL) and DMF (1.5 mL) and the mixture is heated to 75° C. After stirring for 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 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 (0.2799 g, 0.0032 mol), lithium carbonate (0.2286 g, 0.0031 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 an oil. The oil is chromatographed on silica gel (100 mL) using dichloromethane (100%) to give 0.3139 g (72%) of the title compound. An aliquot (0.0391) is recrystallized from dichloromethane/methanol/hexane to give 0.0272 g of product; MS (ESI−) for C19H14ClNO m/z 306.0 (M−H)−; IR (drift) 1470, 1452, 1334, 1293, 1284, 1266, 1231, 1146, 1112, 885, 796, 777, 746, 717, 702 cm−1; 1H NMR (CDCl3) δ5.41, 5.49, 6.60, 6.97, 7.13, 7.28, 7.35, 8.33. Anal. Calcd for C19H14ClNO: C, 74.15; H, 4.59; N, 4.55; Cl, 11.52. Found: C, 73.07; H, 4.63; N, 4.59.

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 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 an oil
  12. customThe oil is chromatographed on silica gel (100 mL)

Sources & evidence

ORD record
ord-c8e8c596a1c9414a864fd46bd6a4b8ff
Source dataset
uspto-grants-2003_02
Patent number
US06514968B1

Reaction notes

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