Nitrogen → Bromo-8-phenyl-8H-8,12b-diazabenzo[a]aceanthrylene

HRID 1485589Notes

Reaction equation

HRID 1485589 reaction equation
[Br:1][C:2]1[CH:21]=[CH:20][C:5]2[N:6]3[C:19]4[C:18]([C:4]=2[CH:3]=1)=[CH:17][CH:16]=[CH:15][C:14]=4[NH:13][C:12]1[C:7]3=[CH:8][CH:9]=[CH:10][CH:11]=1.[C:22]1(N)[CH:27]=CC=[CH:24][CH:23]=1.N#N.P(C(C)(C)C)(C(C)(C)C)C(C)(C)C.CC([O-])(C)C.[Na+].O1[CH2:55][CH2:54]OCC1>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.O>[Br:1][C:2]1[C:3]2[N:6]3[C:19]4[C:18]([C:4]=2[CH:5]=[CH:20][CH:21]=1)=[CH:17][CH:16]=[CH:15][C:14]=4[N:13]([C:55]1[CH:54]=[CH:24][CH:23]=[CH:22][CH:27]=1)[C:12]1[C:7]3=[CH:8][CH:9]=[CH:10][CH:11]=1

Participants

9

Reactant 6

HCID 947NitrogenHCID 6115AnilineHCID 312751,4-DioxaneHCID 83681Tris(1,1-dimethylethyl)phosphineHCID 23676156Sodium t-butoxideHCID 673253603-Bromo-8H-8,12b-diazabenzo[a]aceanthrylene

Product 1

HCID 67325382Bromo-8-phenyl-8H-8,12b-diazabenzo[a]aceanthrylene

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 962WaterSolvent

Procedure

A degassed solution of 30 g (86.6 mmol) of 3-bromo-8H-8,12b-diazabenzo-[a]aceanthrylene and 8.8 g (95.9 mmol) of phenylamine in 1 l of dioxane is saturated with N2 for 1 h. Then, firstly 0.9 ml (4.3 mmol) of P(tBu)3, then 0.480 g (2.1 mmol) of palladium 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, 1 l of water is carefully added. The organic phase is washed with 4×50 ml of H2O and dried over MgSO4, and the solvents are removed in vacuo. The pure product is obtained by recrystallisation. The yield is 27 g (64 mmol), corresponding to 76% of theory.

Workup

  1. temperatureThe reaction mixture is heated
  2. temperatureunder reflux for 18 h
  3. washThe organic phase is washed with 4×50 ml of H2O
  4. dry with materialdried over MgSO4
  5. customthe solvents are removed in vacuo
  6. customThe pure product is obtained by recrystallisation

Sources & evidence

ORD record
ord-875ae68106d94b90860c9c49b6eec3c5
Source dataset
uspto-grants-2016_08
Patent number
US09422287B2

Reaction notes

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