Toluene → 4-(4-Morpholino-3-nitrophenyl)morpholine

HRID 1431220Notes

Reaction equation

HRID 1431220 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([N:8]2[CH2:13][CH2:12][O:11][CH2:10][CH2:9]2)=[C:4]([N+:14]([O-:16])=[O:15])[CH:3]=1.[NH:17]1[CH2:22][CH2:21][O:20][CH2:19][CH2:18]1.CC(C1C=C(C(C)C)C(C2C=CC=CC=2P(C2CCCCC2)C2CCCCC2)=C(C(C)C)C=1)C.CC(C)([O-])C.[Na+].C1(C)C=CC=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.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[N+:14]([C:4]1[CH:3]=[C:2]([N:17]2[CH2:22][CH2:21][O:20][CH2:19][CH2:18]2)[CH:7]=[CH:6][C:5]=1[N:8]1[CH2:13][CH2:12][O:11][CH2:10][CH2:9]1)([O-:16])=[O:15]

Participants

7

Reactant 5

HCID 1140TolueneHCID 8083MorpholineHCID 83701685-Bromo-2-morpholinonitrobenzeneHCID 111557942-Dicyclohexylphosphino-2',4',6'-triisoprophylbiphenylHCID 23676156Sodium t-butoxide

Product 1

HCID 596314194-(4-Morpholino-3-nitrophenyl)morpholine

Reagents, catalysts & solvents 1

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalyst

Procedure

4-(4-Bromo-2-nitrophenyl)morpholine (500 mg, 1.74 mmol), morpholine (0.3 mL, 3.48 mmol), Pd2dba3 (112 mg, 0.12 mmol), X-Phos (125 mg, 261 μmol) and sodium tert-butoxide were suspended in toluene (71.0 mL, 666 mmol) and heated at reflux for 2 h. After this time the reaction was cooled to rt and evaporated in vacuo. The residue was taken up in EtOAc (80 mL) and washed with NaHCO3 (satd aq. solution, 40 mL) and brine (40 mL). The separated organic layer was dried over magnesium sulfate, filtered and evaporated in vacuo. Column chromatography (hexanes:EtOAc, 1:0 to 1:2) gave 4,4′-(2-nitro-1,4-phenylene)dimorpholine. Mass Spectrum (ESI) m/e=294.2 (M+1).

Workup

  1. temperatureheated
  2. temperatureat reflux for 2 h
  3. customevaporated in vacuo
  4. washwashed with NaHCO3 (satd aq. solution, 40 mL) and brine (40 mL)
  5. dry with materialThe separated organic layer was dried over magnesium sulfate
  6. filtrationfiltered
  7. customevaporated in vacuo

Sources & evidence

ORD record
ord-3999ee1ffa0542a5b4cb13202929c57f
Source dataset
uspto-grants-2015_01
Patent number
US08940724B2

Reaction notes

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