Diphenylamine → 9,9-Diethyl-2-diphenylaminofluorene

HRID 720016Notes

Reaction equation

HRID 720016 reaction equation
Br[C:2]1[CH:14]=[CH:13][C:12]2[C:11]3[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=3)[C:5]([CH2:17][CH3:18])([CH2:15][CH3:16])[C:4]=2[CH:3]=1.[C:19]1([NH:25][C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1.CC(C)([O-])C.[Na+]>C1(C)C=CC=CC=1.C(OCC)C.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>[CH2:15]([C:5]1([CH2:17][CH3:18])[C:4]2[CH:3]=[C:2]([N:25]([C:26]3[CH:27]=[CH:28][CH:29]=[CH:30][CH:31]=3)[C:19]3[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=3)[CH:14]=[CH:13][C:12]=2[C:11]2[C:6]1=[CH:7][CH:8]=[CH:9][CH:10]=2)[CH3:16]

Participants

8

Reactant 3

HCID 11487DiphenylamineHCID 121238752-Bromo-9,9-diethylfluoreneHCID 23676156Sodium t-butoxide

Product 1

HCID 219021849,9-Diethyl-2-diphenylaminofluoreneYield 98.3%

Reagents, catalysts & solvents 4

HCID 634876Binap, (A+-)-CatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolventHCID 3283Diethyl EtherSolvent

Procedure

A mixture of 2-bromo-9,9-diethylfluorene (2.44 g, 8.10 mmol), diphenylamine (1.43 g, 8.5 mmol), tris(dibenzylideneacetone)dipalladium (0.018 g, 0.25 mmol %), rac-BINAP (0.037 g, 0.75 mmol %), and sodium t-butoxide (1.08 g, 11.34 mmol) in dry toluene (100 ml) was heated at the refluxing temperature of the solvent for 8–10 h under an atmospheric pressure of nitrogen. After cooling the reaction mixture to room temperature, it was diluted with diethylether (60 ml), washed with brine (40 ml) and water. Organic layer was dried over sodium sulfate and concentrated in vacuuo. The crude product was purified by column chromatography (silica gel, hexane-toluene/9:1 as eluent, Rf=0.6 on thin layer chromatography using hexane-toluene/4:1 as eluent) to give 9,9-diethyl-2-diphenylaminofluorene (3.1 g) as a white amorphous low melting solid in a yield of 98%.

Workup

  1. temperaturewas heated at the refluxing temperature of the solvent for 8–10 h under an atmospheric pressure of nitrogen
  2. washwashed with brine (40 ml) and water
  3. dry with materialOrganic layer was dried over sodium sulfate
  4. concentrationconcentrated in vacuuo
  5. customThe crude product was purified by column chromatography (silica gel, hexane-toluene/9:1 as eluent, Rf=0.6 on thin layer chromatography using hexane-toluene/4:1 as eluent)

Sources & evidence

ORD record
ord-f7d24ea3c75e4670aa8f3f3dfc39c945
Source dataset
uspto-grants-2006_11
Patent number
US07132572B2

Reaction notes

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