Morpholine → 4-(2-Methoxy-5-nitrophenyl)morpholine

HRID 271106Notes

Reaction equation

HRID 271106 reaction equation
Br[C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=[CH:4][C:3]=1[O:11][CH3:12].[NH:13]1[CH2:18][CH2:17][O:16][CH2:15][CH2:14]1.C(=O)([O-])[O-].[Cs+].[Cs+]>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C1C=CC(P(C2C(C3C(P(C4C=CC=CC=4)C4C=CC=CC=4)=CC=C4C=3C=CC=C4)=C3C(C=CC=C3)=CC=2)C2C=CC=CC=2)=CC=1.O1CCOCC1>[CH3:12][O:11][C:3]1[CH:4]=[CH:5][C:6]([N+:8]([O-:10])=[O:9])=[CH:7][C:2]=1[N:13]1[CH2:18][CH2:17][O:16][CH2:15][CH2:14]1

Participants

7

Reactant 3

HCID 8083MorpholineHCID 10796Cesium carbonateHCID 788702-Bromo-4-nitroanisole

Product 1

HCID 223531674-(2-Methoxy-5-nitrophenyl)morpholineYield 40.9%

Reagents, catalysts & solvents 3

HCID 634876Binap, (A+-)-CatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
80 °C

Procedure

2-Bromo-1-methoxy-4-nitro-benzene (810 mg, 4 mmol), morpholine (420 μL, 4.8 mmol), cesium carbonate (1.8 g, 5.6 mmol), Pd2(dba)3 (75 mg, 0.02 mmol) and BINAP (75 mg, 0.03 mmol) were added to 5 mL dry dioxane under an argon atmosphere and heated to 80° C. for 6 hours. After cooling, the solvent was evaporated and the residue was purified by silica gel chromatagraphy (eluent: 5% MeOH/DCM) to afford 390 mg 4-(2-methoxy-5-nitro-phenyl)-morpholine (w): m/e: 238.09, MS (ES+): 239.3; 1H NMR (500 MHz, CDCl3): 8.0 (d, J=10 Hz, 1H), 7.8 (s, 1H), 6.9 (d, J=10 Hz, 1H), 4.1 (s, 3H), 3.9 (m, 4H) and 3.2 (m, 4H).

Workup

  1. temperatureAfter cooling
  2. customthe solvent was evaporated
  3. customthe residue was purified by silica gel chromatagraphy (eluent: 5% MeOH/DCM)

Sources & evidence

ORD record
ord-787c2446489c43e9a349cdfc5d013469
Source dataset
uspto-grants-2008_11
Patent number
US07452873B2

Reaction notes

Loading…