2-Aminobiphenyl → N-((1,1'-Biphenyl)-2-yl)-9,9-dimethyl-9H-fluoren-2-amine

HRID 628216Notes

Reaction equation

HRID 628216 reaction equation
CC(C)([O-])C.[Na+].[C:7]1([C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)[CH:12]=[CH:11][CH:10]=[CH:9][C:8]=1[NH2:13].Br[C:21]1[CH:33]=[CH:32][C:31]2[C:30]3[C:25](=[CH:26][CH:27]=[CH:28][CH:29]=3)[C:24]([CH3:35])([CH3:34])[C:23]=2[CH:22]=1>C1(C)C=CC=CC=1.C1(P(C2C=CC=CC=2)[C-]2C=CC=C2)C=CC=CC=1.[C-]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C1.[Fe+2].C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[C:7]1([C:14]2[CH:15]=[CH:16][CH:17]=[CH:18][CH:19]=2)[CH:12]=[CH:11][CH:10]=[CH:9][C:8]=1[NH:13][C:21]1[CH:33]=[CH:32][C:31]2[C:30]3[C:25](=[CH:26][CH:27]=[CH:28][CH:29]=3)[C:24]([CH3:35])([CH3:34])[C:23]=2[CH:22]=1

Participants

7

Reactant 3

HCID 70152-AminobiphenylHCID 109456062-Bromo-9,9-dimethylfluoreneHCID 23676156Sodium t-butoxide

Product 1

HCID 66803057N-((1,1'-Biphenyl)-2-yl)-9,9-dimethyl-9H-fluoren-2-amine

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)CatalystHCID 1140TolueneSolvent2×

Procedure

1,1′-Bis(diphenylphosphino)ferrocene (1.5 g, 2.7 mmol), palladium acetate (616 mg, 2.7 mmol) and sodium tert-butoxide (22.9 g, 238 mmol) are added to a solution of biphenyl-2-ylamine (31.0 g, 183 mmol) and 2-bromo-9,9-dimethyl-9H-fluorene (50.0 g, 183 mmol) in degassed toluene (400 ml), and the mixture is heated under reflux for 20 h. The reaction mixture is cooled to room temperature, diluted with toluene and filtered through Celite. The filtrate is diluted with water and re-extracted with toluene, and the combined organic phases are dried and evaporated in vacuo. The residue is filtered through silica gel (heptane/dichloromethane) and crystallised from isopropanol, giving biphenyl-2-yl-(9,9-dimethyl-9H-fluoren-2-yl)amine in the form of a pale-yellow solid (63.0 g, 95% of theory).

Workup

  1. temperaturethe mixture is heated
  2. temperatureunder reflux for 20 h
  3. filtrationfiltered through Celite
  4. additionThe filtrate is diluted with water
  5. extractionre-extracted with toluene
  6. customthe combined organic phases are dried
  7. customevaporated in vacuo
  8. filtrationThe residue is filtered through silica gel (heptane/dichloromethane)
  9. customcrystallised from isopropanol

Sources & evidence

ORD record
ord-141d5bec10724f79add39cee804b5cf3
Source dataset
uspto-grants-2016_04
Patent number
US09312495B2

Reaction notes

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