4-Bromobiphenyl → 10-Biphenyl-4-yl-12,12-dimethyl-10,12-dihydro-10-azaindeno[2,1-b]fluorene

HRID 2275936Notes

Reaction equation

HRID 2275936 reaction equation
[CH3:1][C:2]1([CH3:22])[C:10]2=[CH:11][C:12]3[NH:13][C:14]4[C:19]([C:20]=3[CH:21]=[C:9]2[C:8]2[C:3]1=[CH:4][CH:5]=[CH:6][CH:7]=2)=[CH:18][CH:17]=[CH:16][CH:15]=4.Br[C:24]1[CH:29]=[CH:28][C:27]([C:30]2[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=2)=[CH:26][CH:25]=1.C(P(C(C)(C)C)C(C)(C)C)(C)(C)C.CC([O-])(C)C.[Na+]>C1(C)C=CC=CC=1.CC([O-])=O.CC([O-])=O.[Pd+2]>[C:27]1([C:30]2[CH:31]=[CH:32][CH:33]=[CH:34][CH:35]=2)[CH:28]=[CH:29][C:24]([N:13]2[C:12]3[CH:11]=[C:10]4[C:2]([CH3:22])([CH3:1])[C:3]5[C:8]([C:9]4=[CH:21][C:20]=3[C:19]3[C:14]2=[CH:15][CH:16]=[CH:17][CH:18]=3)=[CH:7][CH:6]=[CH:5][CH:4]=5)=[CH:25][CH:26]=1

Participants

7

Reactant 4

HCID 71014-BromobiphenylHCID 83681Tris(1,1-dimethylethyl)phosphineHCID 23676156Sodium t-butoxideHCID 665852047,7-Dimethyl-5,7-dihydroindeno[2,1-b]carbazole

Product 1

HCID 6679777010-Biphenyl-4-yl-12,12-dimethyl-10,12-dihydro-10-azaindeno[2,1-b]fluoreneYield 50.8%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 1140TolueneSolvent

Procedure

20 g (70.58 mmol) of 12,12-dimethyl-10,12-dihydro-10-azaindeno[2,1-b]-fluorene and 24.6 g (105.87 mmol) of 4-bromobiphenyl are dissolved in toluene and degassed by introduction of a protective gas. 4.94 ml (4.94 mmol, 1 M solution in toluene) of tri-tert-butylphosphine, 633.8 mg (2.82 mmol) of Pd(OAc)2 and 10.2 g (105.87 mmol) of NaOtBu are subsequently added. The solids are degassed in advance, the reaction mixture is subsequently degassed, and then stirred under reflux for 3 h. The warm reaction solution is filtered through Alox B (activity grade 1), washed with water, dried and evaporated. Crystallisation from toluene gives 15.6 g (50.8%) of the product as a white solid having a purity of 99.7%.

Workup

  1. customdegassed by introduction of a protective gas
  2. customThe solids are degassed in advance
  3. customthe reaction mixture is subsequently degassed
  4. temperatureunder reflux for 3 h
  5. customThe warm reaction solution
  6. filtrationis filtered through Alox B (activity grade 1)
  7. washwashed with water
  8. customdried
  9. customevaporated
  10. customCrystallisation from toluene

Sources & evidence

ORD record
ord-61a3cf4d8c424058a697d9b99d152b0a
Source dataset
uspto-grants-2015_09
Patent number
US09126970B2

Reaction notes

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