2-Bromo-9,9-dimethylfluorene → biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-2-yl)-(12,12-dimethyl-10-phenyl-10,12-dihydro-10-azaindeno[2,1-b]fluoren-7-yl)amine

HRID 2275913Notes

Reaction equation

HRID 2275913 reaction equation
[Cl-].C(PC(C)(C)C)(C)(C)C.[C:11]1([C:46]2[CH:51]=[CH:50][CH:49]=[CH:48][CH:47]=2)[CH:16]=[CH:15][C:14]([NH:17][C:18]2[CH:19]=[C:20]3[C:28](=[CH:29][CH:30]=2)[N:27]([C:31]2[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=2)[C:26]2[CH:25]=[C:24]4[C:37]([CH3:45])([CH3:44])[C:38]5[C:43]([C:23]4=[CH:22][C:21]3=2)=[CH:42][CH:41]=[CH:40][CH:39]=5)=[CH:13][CH:12]=1.Br[C:53]1[CH:65]=[CH:64][C:63]2[C:62]3[C:57](=[CH:58][CH:59]=[CH:60][CH:61]=3)[C:56]([CH3:67])([CH3:66])[C:55]=2[CH:54]=1.CC(C)([O-])C.[Na+]>C1(C)C=CC=CC=1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.O>[C:11]1([C:46]2[CH:47]=[CH:48][CH:49]=[CH:50][CH:51]=2)[CH:16]=[CH:15][C:14]([N:17]([C:53]2[CH:65]=[CH:64][C:63]3[C:62]4[C:57](=[CH:58][CH:59]=[CH:60][CH:61]=4)[C:56]([CH3:67])([CH3:66])[C:55]=3[CH:54]=2)[C:18]2[CH:19]=[C:20]3[C:28](=[CH:29][CH:30]=2)[N:27]([C:31]2[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=2)[C:26]2[CH:25]=[C:24]4[C:37]([CH3:44])([CH3:45])[C:38]5[C:43]([C:23]4=[CH:22][C:21]3=2)=[CH:42][CH:41]=[CH:40][CH:39]=5)=[CH:13][CH:12]=1

Participants

8

Reactant 4

HCID 109456062-Bromo-9,9-dimethylfluoreneHCID 22613607Di-tert-butylphosphine chlorideHCID 23676156Sodium t-butoxideHCID 66798015Biphenyl-4-yl-(12,12-dimethyl-10-phenyl-10,12-dihydro-10-azaindeno[2,1-b]fluoren-7-yl)amine

Product 1

HCID 66798022biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-2-yl)-(12,12-dimethyl-10-phenyl-10,12-dihydro-10-azaindeno[2,1-b]fluoren-7-yl)amine

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 962WaterSolventHCID 1140TolueneSolvent

Conditions

Temperature
60 °C

Procedure

190 μl (1 mmol) of di-tert-butylphosphine chloride and then 112 mg (0.5 mmol) of palladium(II)acetate are added to a suspension of 26.3 g (50 mmol) of biphenyl-4-yl-(12,12-dimethyl-10-phenyl-10,12-dihydro-10-azaindeno[2,1-b]fluoren-7-yl)amine, 13.3 g (49 mmol) of 2-bromo-9,9-dimethylfluorene and 7.7 g (80 mmol) of sodium tert-butoxide in 500 ml of toluene, and the mixture is subsequently heated under reflux for 5 h. After cooling to 60° C., 500 ml of water are added, the organic phase is separated off, filtered through silica gel, evaporated virtually to dryness under reduced pressure at 80° C., and 300 ml of ethanol are then added. After cooling, the solid is filtered off with suction and then recrystallised five times from dioxane. Yield: 31.5 g (43 mmol), 88%, purity 99.9% (HPLC).

Workup

  1. temperaturethe mixture is subsequently heated
  2. temperatureunder reflux for 5 h
  3. customthe organic phase is separated off
  4. filtrationfiltered through silica gel
  5. customevaporated virtually to dryness under reduced pressure at 80° C.
  6. addition300 ml of ethanol are then added
  7. temperatureAfter cooling
  8. filtrationthe solid is filtered off with suction
  9. customrecrystallised five times from dioxane

Sources & evidence

ORD record
ord-55cc86af3c004dfa847c5ec57651f3a0
Source dataset
uspto-grants-2015_09
Patent number
US09126970B2

Reaction notes

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