Toluene → 7-bromo-9,9-dimethyl-N,N-di-p-tolyl-9H-fluoren-2-amine

HRID 1755525Notes

Reaction equation

HRID 1755525 reaction equation
Br[C:2]1[CH:14]=[CH:13][C:12]2[C:11]3[C:6](=[CH:7][C:8]([Br:15])=[CH:9][CH:10]=3)[C:5]([CH3:17])([CH3:16])[C:4]=2[CH:3]=1.[C:18]1(C)[CH:23]=[CH:22][CH:21]=[CH:20][C:19]=1[NH:24][C:25]1[CH:30]=CC=C[C:26]=1C.[CH3:33][C:34]([CH3:37])([O-])[CH3:35].[Na+].[C:39]1(C)C=CC=CC=1>C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[Br:15][C:8]1[CH:7]=[C:6]2[C:11]([C:12]3[CH:13]=[CH:14][C:2]([N:24]([C:19]4[CH:18]=[CH:23][C:22]([CH3:39])=[CH:21][CH:20]=4)[C:25]4[CH:26]=[CH:35][C:34]([CH3:37])=[CH:33][CH:30]=4)=[CH:3][C:4]=3[C:5]2([CH3:16])[CH3:17])=[CH:10][CH:9]=1

Participants

6

Reactant 4

HCID 1140TolueneHCID 136423Benzenamine, 2-methyl-N-(2-methylphenyl)-HCID 121238762,7-Dibromo-9,9-dimethylfluoreneHCID 23676156Sodium t-butoxide

Product 1

HCID 867120537-bromo-9,9-dimethyl-N,N-di-p-tolyl-9H-fluoren-2-amineYield 66.6%

Reagents, catalysts & solvents 1

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)Catalyst

Conditions

Temperature
80 °C

Procedure

A mixture of 2,7-dibromo-9,9-dimethyl-9H-fluorene (31.64 g, 89.87 mmol), ditolylamine (8.865 g, 44.9 mmol), Pd(dppf)Cl2 (1.644 g, 2.25 mmol) and sodium tert-butoxide (10.796 g, 112.3 mmol) in toluene 400 mL was degassed and heated at about 80° C. overnight. The resulting mixture was poured into ethyl acetate (500 mL). After the precipitate was filtered off, the solution was washed with water and brine, dried over Na2SO4, loaded on silica gel and purified by flash column (hexane to hexanes/dichloromethane 99:1 to 95:5 gradients). After removal of solvent and recrystallization in dichloromethane/hexanes, a white solid (Compound 32) was obtained (14.0169 g, in 66.6% yield).

Workup

  1. customwas degassed
  2. additionThe resulting mixture was poured into ethyl acetate (500 mL)
  3. filtrationAfter the precipitate was filtered off
  4. washthe solution was washed with water and brine
  5. dry with materialdried over Na2SO4
  6. custompurified by flash column (hexane to hexanes/dichloromethane 99:1 to 95:5 gradients)
  7. customAfter removal of solvent and recrystallization in dichloromethane/hexanes

Sources & evidence

ORD record
ord-dbcc9cdabf984bc6a8ebafc47ca3c079
Source dataset
uspto-grants-2015_10
Patent number
US09172051B2

Reaction notes

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