Cesium carbonate → Ethyl 4-[(6a-methyl-5,6,6a,7,8,9-hexahydro-4H-2-phenalenyl)amino]benzoate

HRID 1097392Notes

Reaction equation

HRID 1097392 reaction equation
[CH3:1][C:2]12[C:14]3[C:6](=[CH:7][C:8]([NH2:15])=[CH:9][C:10]=3[CH2:11][CH2:12][CH2:13]1)[CH2:5][CH2:4][CH2:3]2.I[C:17]1[CH:27]=[CH:26][C:20]([C:21]([O:23][CH2:24][CH3:25])=[O:22])=[CH:19][CH:18]=1.C(=O)([O-])[O-].[Cs+].[Cs+]>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].C1(P(C2C=CC=CC=2)C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[CH3:1][C:2]12[C:14]3[C:6](=[CH:7][C:8]([NH:15][C:17]4[CH:27]=[CH:26][C:20]([C:21]([O:23][CH2:24][CH3:25])=[O:22])=[CH:19][CH:18]=4)=[CH:9][C:10]=3[CH2:11][CH2:12][CH2:13]1)[CH2:5][CH2:4][CH2:3]2

Participants

7

Reactant 3

HCID 10796Cesium carbonateHCID 142891Ethyl 4-iodobenzoateHCID 58420583HCID 58420583, compound

Product 1

HCID 25190221Ethyl 4-[(6a-methyl-5,6,6a,7,8,9-hexahydro-4H-2-phenalenyl)amino]benzoateYield 52.9%

Reagents, catalysts & solvents 3

HCID 634876Binap, (A+-)-CatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolvent

Conditions

Temperature
80 °C

Procedure

6a-Methyl-5,6,6a,7,8,9-hexahydro-4H-2-phenalenylamine (0.290 g) and ethyl 4-iodobenzoate (0.390 g) were dissolved in anhydrous toluene (5 ml), the solution was added with tris(dibenzylideneacetone)dipalladium (0.026 g), (±)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (0.036 g), and cesium carbonate (0.493 g), and the mixture was stirred overnight at 80° C. under an argon flow. The reaction mixture was left to cool and then poured into ice water, and the mixture was extracted with diethyl ether. The organic layer was washed successively with 2 N aqueous hydrochloric acid, water and saturated brine, and dried over anhydrous sodium sulfate. The organic layer was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography (developing solvent: ethyl acetate:n-hexane=1:50) to obtain the title compound (0.261 g, yield: 52%). The compound was recrystallized from chloroform-n-hexane to obtain colorless needles (melting point: 135-137° C.).

Workup

  1. waitThe reaction mixture was left
  2. temperatureto cool
  3. extractionthe mixture was extracted with diethyl ether
  4. washThe organic layer was washed successively with 2 N aqueous hydrochloric acid, water and saturated brine
  5. dry with materialdried over anhydrous sodium sulfate
  6. concentrationThe organic layer was concentrated under reduced pressure
  7. customthe resulting residue was purified by silica gel column chromatography (developing solvent: ethyl acetate:n-hexane=1:50)

Sources & evidence

ORD record
ord-ccffdc5ff9dc44219cb762e6bf78a3bd
Source dataset
uspto-grants-2012_03
Patent number
US08143260B2

Reaction notes

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