Morpholine → 4-(4-Methyl-3-nitrophenyl)morpholine

HRID 912325Notes

Reaction equation

HRID 912325 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([CH3:8])=[C:4]([N+:9]([O-:11])=[O:10])[CH:3]=1.P([O-])([O-])([O-])=O.[K+].[K+].[K+].[NH:20]1[CH2:25][CH2:24][O:23][CH2:22][CH2:21]1.COC1C=CC=C(OC)C=1C1C=CC=CC=1P(C1CCCCC1)C1CCCCC1>[Pd].[Pd].C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1.C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1.C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1.O.CN(C=O)C>[CH3:8][C:5]1[CH:6]=[CH:7][C:2]([N:20]2[CH2:25][CH2:24][O:23][CH2:22][CH2:21]2)=[CH:3][C:4]=1[N+:9]([O-:11])=[O:10]

Participants

8

Reactant 4

HCID 8083MorpholineHCID 62657Potassium Phosphate, TribasicHCID 1235464-Bromo-2-nitrotolueneHCID 112698722-Dicyclohexylphosphino-2',6'-dimethoxybiphenyl

Product 1

HCID 219558884-(4-Methyl-3-nitrophenyl)morpholineYield 93%

Reagents, catalysts & solvents 3

HCID 9832798Tris(dibenzylideneacetone) dipalladiumCatalystHCID 962WaterSolventHCID 6228DimethylformamideSolvent

Conditions

Temperature
110 °C

Procedure

To 4-bromo-1-methyl-2-nitro-benzene (500 mg), tris (dibenzylideneacetone) dipalladium (120 mg) and potassium phosphate (928 mg), morpholine (242 mg), S-Phos (95 mg) and deaerated DMF (5 ml) were added, followed by irradiation of ultrasonic wave for 5 minutes. This was stirred at 110° C. for 5 hours. After cooling to room temperature, water was added, followed by extraction with ethyl acetate, and the organic layer was washed with brine, and dried over magnesium sulfate. After the magnesium sulfate was filtered off, the solvent was distilled off under reduced pressure, followed by purification by silica gel column chromatography (hexane/ethyl acetate=4/1), to obtain the desired compound as an orange solid (478 mg, 93%).

Workup

  1. customfollowed by irradiation of ultrasonic wave for 5 minutes
  2. temperatureAfter cooling to room temperature
  3. extractionfollowed by extraction with ethyl acetate
  4. washthe organic layer was washed with brine
  5. dry with materialdried over magnesium sulfate
  6. filtrationAfter the magnesium sulfate was filtered off
  7. distillationthe solvent was distilled off under reduced pressure
  8. customfollowed by purification by silica gel column chromatography (hexane/ethyl acetate=4/1)

Sources & evidence

ORD record
ord-9312813d7702407891d8bb4a7fc8f9ea
Source dataset
uspto-grants-2011_09
Patent number
US08022205B2

Reaction notes

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