Trifluoroacetic acid → 5-Methyl-1-phenyl-1,2-dihydro[1,4]oxazino[2,3,4-jk]carbazol-7-ol

HRID 1279708Notes

Reaction equation

HRID 1279708 reaction equation
[CH3:1][C:2]1[CH:3]=[C:4]2[C:12]3=[C:13]([O:15][CH2:16][CH:17]([C:18]4[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=4)[N:11]3[C:10]3[CH2:9][CH2:8][CH2:7][C:6](=[O:24])[C:5]2=3)[CH:14]=1.FC(F)(F)C(O)=O.[Br-].[Li+].C(=O)([O-])[O-].[Li+].[Li+]>C(OCC)(=O)C.C(#N)C.C(Cl)Cl>[CH3:1][C:2]1[CH:3]=[C:4]2[C:12]3=[C:13]([O:15][CH2:16][CH:17]([C:18]4[CH:19]=[CH:20][CH:21]=[CH:22][CH:23]=4)[N:11]3[C:10]3[C:5]2=[C:6]([OH:24])[CH:7]=[CH:8][CH:9]=3)[CH:14]=1

Participants

7

Reactant 4

HCID 6422Trifluoroacetic acidHCID 11125Lithium CarbonateHCID 82050Lithium BromideHCID 121486325-methyl-1-phenyl-1,2,9,10-tetrahydro[1,4]oxazino[2,3,4-jk]carbazol-7(8H)-one

Product 1

HCID 121486335-Methyl-1-phenyl-1,2-dihydro[1,4]oxazino[2,3,4-jk]carbazol-7-olYield 14.5%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 21930812Acetonitrile ethyl acetateSolvent

Conditions

Temperature
90 °C

Procedure

To 5-methyl-1-phenyl-1,2,9,10-tetrahydro[1,4]oxazino[2,3,4-jk]carbazol-7(8H)-one (9.0 g, 28.4 mmol) in ethyl acetate/acetonitrile (150 mL/50 mL) is added trifluoroacetic acid (4 mL) and anhydrous cupric chloride (9.7 g, 56.7 mmol). The mixture is heated to reflux at 90° C. for 7 h. The mixture is poured into methylene chloride (500 mL) and filtered to remove inorganic solids. The filtrates are washed with saturated potassium carbonate solution followed by water, dried over magnesium sulfate and concentrated. The residue is dissolved in DMF (20 mL) to which is added lithium bromide (4.2 g, 56.7 mmol) and lithium carbonate (4.9 g, 56.7 mmol). The mixture is heated at 119° C. for 5 h, then partitioned between water and CH2Cl2. The organic layer is washed twice with brine (30 mL). Column chromatography (200 g silica gel) using EtOAc/hexanes (20/80) as eluent gave 1.3 g (14.5%) of 5-methyl-1-phenyl-1,2-dihydro[1,4]oxazino[2,3,4-jk]carbazol-7-ol.

Workup

  1. temperatureThe mixture is heated
  2. filtrationfiltered
  3. customto remove inorganic solids
  4. washThe filtrates are washed with saturated potassium carbonate solution
  5. dry with materialdried over magnesium sulfate
  6. concentrationconcentrated
  7. dissolutionThe residue is dissolved in DMF (20 mL) to which
  8. temperatureThe mixture is heated at 119° C. for 5 h
  9. custompartitioned between water and CH2Cl2
  10. washThe organic layer is washed twice with brine (30 mL)

Sources & evidence

ORD record
ord-04e24e47ffd64a4bbcc39a07ab898ec0
Source dataset
uspto-grants-2002_09
Patent number
US06448397B1

Reaction notes

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