Nitrogen → N-((1,1'-Biphenyl)-4-yl)-N-(4-bromophenyl)-9,9-dimethyl-9H-fluoren-2-amine

HRID 2277360Notes

Reaction equation

HRID 2277360 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5](I)=[CH:4][CH:3]=1.[C:9]1([C:31]2[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=2)[CH:14]=[CH:13][C:12]([NH:15][C:16]2[CH:28]=[CH:27][C:26]3[C:25]4[C:20](=[CH:21][CH:22]=[CH:23][CH:24]=4)[C:19]([CH3:30])([CH3:29])[C:18]=3[CH:17]=2)=[CH:11][CH:10]=1.N#N.P(C(C)(C)C)(C(C)(C)C)C(C)(C)C.CC([O-])(C)C.[Na+]>O1CCOCC1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.O>[C:9]1([C:31]2[CH:32]=[CH:33][CH:34]=[CH:35][CH:36]=2)[CH:14]=[CH:13][C:12]([N:15]([C:5]2[CH:6]=[CH:7][C:2]([Br:1])=[CH:3][CH:4]=2)[C:16]2[CH:28]=[CH:27][C:26]3[C:25]4[C:20](=[CH:21][CH:22]=[CH:23][CH:24]=4)[C:19]([CH3:30])([CH3:29])[C:18]=3[CH:17]=2)=[CH:11][CH:10]=1

Participants

9

Reactant 5

HCID 947NitrogenHCID 115221-Bromo-4-iodobenzeneHCID 83681Tris(1,1-dimethylethyl)phosphineHCID 20730584N-(biphenyl-4-yl)-9,9-dimethyl-9H-fluoren-2-amineHCID 23676156Sodium t-butoxide

Product 1

HCID 58131689N-((1,1'-Biphenyl)-4-yl)-N-(4-bromophenyl)-9,9-dimethyl-9H-fluoren-2-amine

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 962WaterSolventHCID 312751,4-DioxaneSolvent

Procedure

A degassed solution of 24.6 g (87 mmol) of 1-bromo-4-iodobenzene and 28.8 g (80 mmol) of biphenyl-4-yl-(9,9-dimethyl-9H-fluoren-2-yl)amine in 1000 ml of dioxane is saturated with N2 for 1 h. Then firstly 0.9 ml (4.3 mmol) of P(tBu)3, then 0.48 g (2.1 mmol) of palladium(II) acetate are added to the solution. 12.6 g (131 mmol) of NaOtBu in the solid state are subsequently added. The reaction mixture is heated under reflux for 18 h. After cooling to room temperature, 1000 ml of water are carefully added. The organic phase is washed with 4×50 ml of water and dried over MgSO4, and the solvent is removed in vacuo. The pure product is obtained by recrystallisation and final sublimation.

Workup

  1. temperatureThe reaction mixture is heated
  2. temperatureunder reflux for 18 h
  3. washThe organic phase is washed with 4×50 ml of water
  4. dry with materialdried over MgSO4
  5. customthe solvent is removed in vacuo
  6. customThe pure product is obtained by recrystallisation

Sources & evidence

ORD record
ord-9263e7a3cf0941c0832e49c49cecac84
Source dataset
uspto-grants-2015_09
Patent number
US09133119B2

Reaction notes

Loading…