Lithium Carbonate → HCID 12148621, compound

HRID 1279687Notes

Reaction equation

HRID 1279687 reaction equation
[C:1]1([C@@H:7]2[N:21]3[C:22]4[C:14]([C:15]5[C:16](=[O:23])[CH2:17][CH2:18][CH2:19][C:20]=53)=[CH:13][CH:12]=[CH:11][C:10]=4[O:9][CH2:8]2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.C(O)(=O)C.O.C(=O)([O-])[O-].[Li+].[Li+].[Cl-].[Li+]>CN(C=O)C>[C:1]1([C@@H:7]2[N:21]3[C:22]4[C:14]([C:15]5[C:20]3=[CH:19][CH:18]=[CH:17][C:16]=5[OH:23])=[CH:13][CH:12]=[CH:11][C:10]=4[O:9][CH2:8]2)[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=1

Participants

6

Reactant 4

HCID 11125Lithium CarbonateHCID 433294Lithium ChlorideHCID 12148620HCID 12148620, compoundHCID 21899381Acetic acid--water (1/1)

Product 1

HCID 12148621HCID 12148621, compound

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
120 °C

Procedure

A mixture of (S)-(+)-1-phenyl-1,2,9,10-tetrahydro[1,4]oxazino[2,3,4-jk]carbazol-7(8H)-one (0.397 g, 1.31 mmol), cupric chloride dihydrate (0.513 g, 3.01 mmol), and acetic acid/water (1:1, 4 mL) is heated at 120° C. for 6 h. After cooling, the mixture is partitioned between dichloromethane, water, and aq. sodium bicarbonate. The organic layers are filtered through sodium sulfate, concentrated, and stored over the weekend in the freezer. The mixture is then stirred at 130-140° C. with lithium carbonate (0.106 g, 1.44 mmol), lithium chloride (0.061 g, 1.44 mmol), and DMF (3 mL). After cooling, the mixture is partitioned between dichloromethane and sat'd aq. ammonium chloride. The organic layers are dried over sodium sulfate, concentrated, and the residue is chromatographed on silica gel gel (60 mL) using ethyl acetate/hexane (10/90) to give 0.184 g (47% for both steps) of (S)-(+)-1-phenyl-1,2-dihydro[1,4]oxazino[2,3,4-jk]carbazol-7-ol. [α]D=+98°(MeOH).

Workup

  1. temperatureAfter cooling
  2. customthe mixture is partitioned between dichloromethane, water, and aq. sodium bicarbonate
  3. filtrationThe organic layers are filtered through sodium sulfate
  4. concentrationconcentrated
  5. temperatureAfter cooling
  6. customthe mixture is partitioned between dichloromethane
  7. dry with materialThe organic layers are dried over sodium sulfate
  8. concentrationconcentrated
  9. customthe residue is chromatographed on silica gel gel (60 mL)

Sources & evidence

ORD record
ord-17f129f43a2d4aa9b9117f95d96719c1
Source dataset
uspto-grants-2002_09
Patent number
US06448397B1

Reaction notes

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