Morpholine → Methyl 4-Morpholinobenzoate

HRID 1296982Notes

Reaction equation

HRID 1296982 reaction equation
[O-]P([O-])([O-])=O.[K+].[K+].[K+].Br[C:10]1[CH:19]=[CH:18][C:13]([C:14]([O:16][CH3:17])=[O:15])=[CH:12][CH:11]=1.[NH:20]1[CH2:25][CH2:24][O:23][CH2:22][CH2:21]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].COCCOC>[C:14]([C:13]1[CH:18]=[CH:19][C:10]([N:20]2[CH2:25][CH2:24][O:23][CH2:22][CH2:21]2)=[CH:11][CH:12]=1)([O:16][CH3:17])=[O:15]

Participants

6

Reactant 3

HCID 8083MorpholineHCID 12081Methyl 4-bromobenzoateHCID 62657Potassium Phosphate, Tribasic

Product 1

HCID 5178200Methyl 4-MorpholinobenzoateYield 80.5%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 80711,2-DimethoxyethaneSolvent

Conditions

Temperature
80 °C

Procedure

An oven-dried resealable Schlenk tube was purged with argon and charged with Pd2(dba)3 (2.3 mg, 0.0025 mmol, 1.0 mol % Pd), 2 [Example 1] (3.0 mg, 0.0076 mmol, 1.5 mol %), K3PO4 (150 mg, 0.71 mmol), and methyl 4-bromobenzoate (108 mg, 0.50 mmol). The tube was purged with argon, fitted with a rubber septum and then DME (1.0 mL) and morpholine (55 μL, 0.63 mmol) were added. The septum was removed, the tube was sealed with a teflon screw cap and the mixture was stirred at 80° C. for 24 h The reaction mixture was then cooled to room temperature, diluted with EtOAc (20 mL), filtered through celite and concentrated in vacua. The crude material was purified by flash chromatography on silica gel to afford 89 mg (80%) of a colorless solid.

Workup

  1. customAn oven-dried resealable Schlenk tube was purged with argon
  2. customThe tube was purged with argon
  3. customfitted with a rubber septum
  4. customThe septum was removed
  5. customthe tube was sealed with a teflon
  6. customscrew cap
  7. temperaturewas then cooled to room temperature
  8. additiondiluted with EtOAc (20 mL)
  9. filtrationfiltered through celite and
  10. concentrationconcentrated in vacua
  11. customThe crude material was purified by flash chromatography on silica gel

Sources & evidence

ORD record
ord-c62ed6acc2434668a4f7892d9962c805
Source dataset
uspto-grants-2007_07
Patent number
US07247731B2

Reaction notes

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