Tris(1,1-dimethylethyl)phosphine → N-(1,1'-Biphenyl)-2-yl-N-(9,9-dimethyl-9H-fluoren-2-yl)-9,9'-spirobi(9H-fluoren)-2-amine

HRID 628217Notes

Reaction equation

HRID 628217 reaction equation
C(P(C(C)(C)C)C(C)(C)C)(C)(C)C.CC(C)([O-])C.[Na+].[C:20]1([C:42]2[CH:47]=[CH:46][CH:45]=[CH:44][CH:43]=2)[CH:25]=[CH:24][CH:23]=[CH:22][C:21]=1[NH:26][C:27]1[CH:39]=[CH:38][C:37]2[C:36]3[C:31](=[CH:32][CH:33]=[CH:34][CH:35]=3)[C:30]([CH3:41])([CH3:40])[C:29]=2[CH:28]=1.Br[C:49]1[CH:61]=[CH:60][C:59]2[C:58]3[C:53](=[CH:54][CH:55]=[CH:56][CH:57]=3)[C:52]3([C:73]4[CH:72]=[CH:71][CH:70]=[CH:69][C:68]=4[C:67]4[C:62]3=[CH:63][CH:64]=[CH:65][CH:66]=4)[C:51]=2[CH:50]=1>C1(C)C=CC=CC=1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[C:20]1([C:42]2[CH:43]=[CH:44][CH:45]=[CH:46][CH:47]=2)[CH:25]=[CH:24][CH:23]=[CH:22][C:21]=1[N:26]([C:27]1[CH:39]=[CH:38][C:37]2[C:36]3[C:31](=[CH:32][CH:33]=[CH:34][CH:35]=3)[C:30]([CH3:40])([CH3:41])[C:29]=2[CH:28]=1)[C:49]1[CH:61]=[CH:60][C:59]2[C:58]3[C:53](=[CH:54][CH:55]=[CH:56][CH:57]=3)[C:52]3([C:73]4[CH:72]=[CH:71][CH:70]=[CH:69][C:68]=4[C:67]4[C:62]3=[CH:63][CH:64]=[CH:65][CH:66]=4)[C:51]=2[CH:50]=1

Participants

7

Reactant 4

HCID 83681Tris(1,1-dimethylethyl)phosphineHCID 152875222-Bromo-9,9'-spirobi[9H-fluorene]HCID 23676156Sodium t-butoxideHCID 66803057N-((1,1'-Biphenyl)-2-yl)-9,9-dimethyl-9H-fluoren-2-amine

Product 1

HCID 66803019N-(1,1'-Biphenyl)-2-yl-N-(9,9-dimethyl-9H-fluoren-2-yl)-9,9'-spirobi(9H-fluoren)-2-amine

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 1140TolueneSolvent3×

Procedure

Tri-tert-butylphosphine (4.4 ml of a 1.0 M solution in toluene, 4.4 mmol), palladium acetate (248 mg, 1.1 mmol) and sodium tert-butoxide (16.0 g, 166 mmol) are added to a solution of biphenyl-2-yl-(9,9-dimethyl-9H-fluoren-2-yl)amine (40.0 g, 111 mmol) and 2-bromo-9,9′-spirobifluorene (56.9 g, 144 mmol) in degassed toluene (500 ml), and the mixture is heated under reflux for 2 h. The reaction mixture is cooled to room temperature, diluted with toluene and filtered through Celite. The filtrate is evaporated in vacuo, and the residue is crystallised from ethyl acetate/heptane. The crude product is extracted in a Soxhlet extractor (toluene) and purified by zone sublimation in vacuo twice (p=3×104 mbar, T=298° C.). Biphenyl-2-yl-(9,9-dimethyl-9H-fluoren-2-yl)-(9,9′-spirobifluoren-2-yl)amine is isolated in the form of a pale-yellow solid (20.4 g, 27% of theory, purity >99.99% according to HPLC).

Workup

  1. temperaturethe mixture is heated
  2. temperatureunder reflux for 2 h
  3. filtrationfiltered through Celite
  4. customThe filtrate is evaporated in vacuo
  5. customthe residue is crystallised from ethyl acetate/heptane
  6. extractionThe crude product is extracted in a Soxhlet extractor (toluene)
  7. custompurified by zone sublimation in vacuo twice (p=3×104 mbar, T=298° C.)

Sources & evidence

ORD record
ord-fc92ce0dda664304a0101b5275141113
Source dataset
uspto-grants-2016_04
Patent number
US09312495B2

Reaction notes

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