9,10-Dibromoanthracene → 9,10-bis[N-phenyl-N-(9-phenylcarbazol-3-yl)amino]anthracene

HRID 1038155Notes

Reaction equation

HRID 1038155 reaction equation
Br[C:2]1[C:3]2[C:8]([C:9](Br)=[C:10]3[C:15]=1[CH:14]=[CH:13][CH:12]=[CH:11]3)=[CH:7][CH:6]=[CH:5][CH:4]=2.[C:17]1([NH:23][C:24]2[CH:25]=[CH:26][C:27]3[N:28]([C:37]4[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=4)[C:29]4[C:34]([C:35]=3[CH:36]=2)=[CH:33][CH:32]=[CH:31][CH:30]=4)[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1.[CH3:43][C:44]([CH3:47])([O-])[CH3:45].[Na+].C(P([C:58]([CH3:61])([CH3:60])C)C(C)(C)C)(C)(C)C>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].C1(C)C=CC=CC=1>[C:17]1([N:23]([C:2]2[C:3]3[C:8]([C:9]([N:23]([C:24]4[CH:36]=[CH:35][C:43]5[N:28]([C:60]6[CH:58]=[CH:61][CH:27]=[CH:26][CH:25]=6)[C:29]6[C:45]([C:44]=5[CH:47]=4)=[CH:33][CH:32]=[CH:31][CH:30]=6)[C:17]4[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=4)=[C:10]4[C:15]=2[CH:14]=[CH:13][CH:12]=[CH:11]4)=[CH:7][CH:6]=[CH:5][CH:4]=3)[C:24]2[CH:25]=[CH:26][C:27]3[N:28]([C:37]4[CH:38]=[CH:39][CH:40]=[CH:41][CH:42]=4)[C:29]4[C:34]([C:35]=3[CH:36]=2)=[CH:33][CH:32]=[CH:31][CH:30]=4)[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=1

Participants

7

Reactant 4

HCID 682269,10-DibromoanthraceneHCID 83681Tris(1,1-dimethylethyl)phosphineHCID 23676156Sodium t-butoxideHCID 59815954N,9-Diphenyl-9H-carbazol-3-amine

Product 1

HCID 582738369,10-bis[N-phenyl-N-(9-phenylcarbazol-3-yl)amino]anthraceneYield 67%

Reagents, catalysts & solvents 2

HCID 6505921(1E,4E)-1,5-diphenylpenta-1,4-dien-3-one; palladiumCatalystHCID 1140TolueneSolvent2×

Procedure

Into a 100 mL three-neck flask were added 835 mg (2.5 mmol) of 9,10-dibromoanthracene, 1.7 g (5.0 mmol) of N,9-diphenyl-9H-carbazol-3-amine (abbreviation: PCA), and 1.0 g (10 mmol) of sodium-tert-butoxide, and the atmosphere in the flask was substituted by nitrogen. Thereafter, 25 mL of toluene and 0.1 mL of tri(tert-butyl)phosphine (10 wt % hexane solution) were added to the mixture. This mixture was stirred under reduced atmosphere to be degassed. After degassing, 72 mg (0.13 mmol) of bis(dibenzylideneacetone)palladium(0) was added. This mixture was stirred at 80° C. for 5 hours under nitrogen. After the reaction, the mixture was added with about 20 mL of toluene and then washed with water. An aqueous layer was extracted with toluene, and the extracted solution was combined with an organic layer and washed with saturated saline. The organic layer was dried with magnesium sulfate, this mixture was naturally filtered, and the filtrate was concentrated. A solid obtained was purified by silica gel column chromatography (developing solvent; hexane:toluene=7:3). Recrystallization of the obtained solid with a mixed solvent of dichloromethane and hexane gave 1.4 g of 9,10-bis[N-phenyl-N-(9-phenylcarbazol-3-yl)amino]anthracene (abbreviation: PCA2A) as orange powder in 67% yield. By a nuclear magnetic resonance measurement, it was confirmed that this compound was 9,10-bis[N-phenyl-N-(9-phenylcarbazol-3-yl)amino]anthracene (abbreviation: PCA2A).

Workup

  1. customto be degassed
  2. customAfter degassing
  3. stirringThis mixture was stirred at 80° C. for 5 hours under nitrogen
  4. customAfter the reaction
  5. washwashed with water
  6. extractionAn aqueous layer was extracted with toluene
  7. washwashed with saturated saline
  8. dry with materialThe organic layer was dried with magnesium sulfate
  9. filtrationthis mixture was naturally filtered
  10. concentrationthe filtrate was concentrated
  11. customA solid obtained
  12. customwas purified by silica gel column chromatography (developing solvent; hexane:toluene=7:3)
  13. customRecrystallization of the obtained solid with a mixed solvent of dichloromethane and hexane

Sources & evidence

ORD record
ord-038006e9d79649aeaeeffcb0150cf315
Source dataset
uspto-grants-2013_10
Patent number
US08546792B2

Reaction notes

Loading…