Lithium Carbonate → HCID 12148624, compound

HRID 2415803Notes

Reaction equation

HRID 2415803 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.[Cl-].[Li+].[Br-].[Li+].C(=O)([O-])[O-].[Li+].[Li+]>CN(C=O)C.C(OCC)(=O)C.O>[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

8

Reactant 4

HCID 11125Lithium CarbonateHCID 82050Lithium BromideHCID 433294Lithium ChlorideHCID 12148623(R)-(-)-1-phenyl-1,2,9,10-tetrahydro[1,4]oxazino[2,3,4-jk]carbazol-7(8H)-one

Product 1

HCID 12148624HCID 12148624, compoundYield 35%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
60 °C

Procedure

To (R)-(−)-1-phenyl-1,2,9,10-tetrahydro[1,4]oxazino[2,3,4-jk]carbazol-7(8H)-one (17.3 g, 57.3 mmol) in dry DMF (60 mL) is added anhydrous cupric chloride (17.7 g 131.8 mmol) and anhydrous lithium chloride (9.6 g, 229 mmol). The mixture is heated at 60° C. for 40 h. The mixture is then poured into water (600 mL), forming solids. The solids are dissolved in ethyl acetate (50 mL) and filtered to remove inorganic solids. The filtrates are concentrated to dryness and the resulting solids are dissolved in DMF (60 mL), to which is added lithium bromide (12.4 g, 143 mmol) and lithium carbonate (10.6 g, 143 mmol). The mixture is heated at 120° C. for 6 h, cooled, then partitioned between water and CH2Cl2, and the organic layer washed three times with water (200 mL). Column chromatography (600 mL silica) is performed using EtOAc/hexanes (20/80) as eluent. The material is then rechromatographed (600 mL silica) using EtOAc/hexane (20/80) as eluent to give 6.0 g (35%) of (R)-(−)-1-phenyl-1,2-dihydro[1,4]oxazino[2,3,4-jk]carbazol-7-ol; [□]25D=−121° (c 0.73, methylene chloride).

Workup

  1. customforming solids
  2. filtrationfiltered
  3. customto remove inorganic solids
  4. concentrationThe filtrates are concentrated to dryness
  5. dissolutionthe resulting solids are dissolved in DMF (60 mL), to which
  6. temperatureThe mixture is heated at 120° C. for 6 h
  7. temperaturecooled
  8. custompartitioned between water and CH2Cl2
  9. washthe organic layer washed three times with water (200 mL)
  10. customThe material is then rechromatographed (600 mL silica)

Sources & evidence

ORD record
ord-7a82722fa91942e09c36cd24b782adf9
Source dataset
uspto-grants-2004_11
Patent number
US06821970B2

Reaction notes

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