Cesium carbonate → HCID 59442006, compound

HRID 1014221Notes

Reaction equation

HRID 1014221 reaction equation
Cl[C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-])=O)=[C:4]([O:11][CH3:12])[CH:3]=1.[CH3:13][C@H:14]1[CH2:19][O:18][CH2:17][CH2:16][NH:15]1.C(=O)([O-])[O-].[Cs+].[Cs+].CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2>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]>[CH3:13][C@H:14]1[CH2:19][O:18][CH2:17][CH2:16][N:15]1[C:2]1[CH:7]=[CH:6][C:5]([NH2:8])=[C:4]([O:11][CH3:12])[CH:3]=1

Participants

6

Reactant 4

HCID 10796Cesium carbonateHCID 811105-Chloro-2-nitroanisoleHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 12012220(3S)-3-methylmorpholine

Product 1

HCID 59442006HCID 59442006, compoundYield 43%

Reagents, catalysts & solvents 1

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalyst

Conditions

Temperature
100 °C

Procedure

4-chloro-2-(methyloxy)-1-nitrobenzene (6.71 g, 29.7 mmol), (3S)-3-methylmorpholine (Synthetech Inc., 2.0 g, 19.8 mmol), cesium carbonate (13.0 g, 40 mmol), Pd2dba3 (1.83 g, 2.0 mmol), and XANTPHOS (1.73 g, 3.0 mmol) were added to degassed dioxane (200 mL) and heated to 100° C. under a water cooled reflux condenser for 12 hours. The dioxane was removed under reduced pressure and the solids were partitioned between methylene chloride (500 mL) and water (500 mL). The organic layer was dried over sodium sulfate, taken to a residue under reduced pressure, and purified by chromatography on SiO2to give 4-[(3S)-3-methyl-4-morpholinyl]-2-(methyloxy)aniline as a yellow solid (2.46 g, 8.45 mmol, 43% yield). 1H NMR (400 MHz, CDCl3) δ ppm 1.22 (dd, J=6.41, 4.58 Hz, 3 H), 3.22-3.29 (m, J=12.11, 8.03, 4.03, 4.03 Hz, 1 H), 3.31-3.37 (m, 1 H), 3.59-3.69 (m, 1 H), 3.78 (d, J=2.93 Hz, 2H), 3.92 (d, J=4.21 Hz, 4 H), 4.02 (s, 1 H), 6.25 (s, 1 H), 6.32-6.39 (m, 1 H), 7.98 (dd, J=9.34, 4.21 Hz, 1 H).

Workup

  1. customto degassed dioxane (200 mL)
  2. temperaturecooled
  3. temperaturereflux condenser for 12 hours
  4. customThe dioxane was removed under reduced pressure
  5. customthe solids were partitioned between methylene chloride (500 mL) and water (500 mL)
  6. dry with materialThe organic layer was dried over sodium sulfate
  7. custompurified by chromatography on SiO2to

Sources & evidence

ORD record
ord-909aa946dc6343148aafb5aa9c55b92c
Source dataset
uspto-grants-2011_07
Patent number
US07981903B2

Reaction notes

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