Phenyl-1-naphthylamine → N~2~,N~7~-Di(naphthalen-1-yl)-N~2~,N~7~-diphenyl-9H-fluorene-2,7-diamine

HRID 2408316Notes

Reaction equation

HRID 2408316 reaction equation
Br[C:2]1[CH:14]=[CH:13][C:12]2[C:11]3[C:6](=[CH:7][C:8](Br)=[CH:9][CH:10]=3)[CH2:5][C:4]=2[CH:3]=1.[C:16]1([NH:22][C:23]2[C:32]3[C:27](=[CH:28][CH:29]=[CH:30][CH:31]=3)[CH:26]=[CH:25][CH:24]=2)[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1>C1(C)C=CC=CC=1>[C:23]1([N:22]([C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=2)[C:2]2[CH:14]=[CH:13][C:12]3[C:11]4[C:6](=[CH:7][C:8]([N:22]([C:23]5[C:32]6[C:27](=[CH:28][CH:29]=[CH:30][CH:31]=6)[CH:26]=[CH:25][CH:24]=5)[C:16]5[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=5)=[CH:9][CH:10]=4)[CH2:5][C:4]=3[CH:3]=2)[C:32]2[C:27](=[CH:28][CH:29]=[CH:30][CH:31]=2)[CH:26]=[CH:25][CH:24]=1

Participants

4

Reactant 2

HCID 7013Phenyl-1-naphthylamineHCID 1400732,7-Dibromofluorene

Product 1

HCID 58262064N~2~,N~7~-Di(naphthalen-1-yl)-N~2~,N~7~-diphenyl-9H-fluorene-2,7-diamine

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

To a 2-liter three-neck round bottom flask was added anhydrous toluene (1000 mL) by cannula. 2,7-dibromofluorene (50.0 g) was added to this flask, then stirred until all dissolved. N-phenyl-1-naphthylamine (81.14 g) was then added. The reaction vessel was purged with a strong nitrogen flow for 30 minutes, followed by the addition of sodium tert-butoxide (44.5 g) by funnel. Tris(dibenzylideneacetone)dipalladium(0) (5.65 g) was added to the reaction. Tri-tert-butyl phosphine (3.75 g) in anhydrous toluene (20 mL) was added via syringe. The reaction was heated to reflux for 2 hours and reaction completion was confirmed by thin-layer chromatography. The vessel was removed from heat and allowed to cool to room temperature. The reaction solution was filtered through a celite/silica gel plug and solvent was then removed by rotary evaporation. The crude material was initially purified by flash chromatography, followed by sublimation to yield NMR pure product.

Workup

  1. customThe reaction vessel was purged with a strong nitrogen flow for 30 minutes
  2. additionfollowed by the addition of sodium tert-butoxide (44.5 g) by funnel
  3. additionTris(dibenzylideneacetone)dipalladium(0) (5.65 g) was added to the reaction
  4. additionTri-tert-butyl phosphine (3.75 g) in anhydrous toluene (20 mL) was added via syringe
  5. temperatureThe reaction was heated
  6. temperatureto reflux for 2 hours
  7. customreaction completion
  8. customThe vessel was removed
  9. temperaturefrom heat
  10. filtrationThe reaction solution was filtered through a celite/silica gel plug and solvent
  11. customwas then removed by rotary evaporation
  12. customThe crude material was initially purified by flash chromatography
  13. customto yield NMR pure product

Sources & evidence

ORD record
ord-77ade064c7e6460e87a050481e99f7cc
Source dataset
uspto-grants-2014_08
Patent number
US08815639B2

Reaction notes

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