Tris(1,1-dimethylethyl)phosphine → N-(biphenyl-4-yl)-N-(4-tert-butylphenyl)chrysene-3-amine

HRID 868792Notes

Reaction equation

HRID 868792 reaction equation
Br[C:2]1[CH:3]=[CH:4][C:5]2[CH:6]=[CH:7][C:8]3[C:17]([C:18]=2[CH:19]=1)=[CH:16][CH:15]=[C:14]1[C:9]=3[CH:10]=[CH:11][CH:12]=[CH:13]1.[C:20]([C:24]1[CH:29]=[CH:28][C:27]([NH:30][C:31]2[CH:36]=[CH:35][C:34]([C:37]3[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=3)=[CH:33][CH:32]=2)=[CH:26][CH:25]=1)([CH3:23])([CH3:22])[CH3:21].C(P(C(C)(C)C)C(C)(C)C)(C)(C)C.CC(C)([O-])C.[Na+]>CC1C=CC=CC=1C.[Pd].[Pd].C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1.C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1.C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1>[C:34]1([C:37]2[CH:38]=[CH:39][CH:40]=[CH:41][CH:42]=2)[CH:33]=[CH:32][C:31]([N:30]([C:27]2[CH:28]=[CH:29][C:24]([C:20]([CH3:23])([CH3:21])[CH3:22])=[CH:25][CH:26]=2)[C:2]2[CH:3]=[CH:4][C:5]3[CH:6]=[CH:7][C:8]4[C:17]([C:18]=3[CH:19]=2)=[CH:16][CH:15]=[C:14]2[C:9]=4[CH:10]=[CH:11][CH:12]=[CH:13]2)=[CH:36][CH:35]=1

Participants

7

Reactant 4

HCID 83681Tris(1,1-dimethylethyl)phosphineHCID 126709163-BromochryseneHCID 23676156Sodium t-butoxideHCID 58371041N-(4-tert-butylphenyl)biphenyl-4-amine

Product 1

HCID 46240429N-(biphenyl-4-yl)-N-(4-tert-butylphenyl)chrysene-3-amine

Reagents, catalysts & solvents 2

HCID 9832798Tris(dibenzylideneacetone) dipalladiumCatalystHCID 7237O-XyleneSolvent3×

Procedure

In a drybox, 3-bromochrysene (0.869 g, 2.83 mmol) and N-(4-tert-butylphenyl)biphenyl-4-amine (0.9 g, 2.97 mmol) were combined in a thick-walled glass tube and dissolved in 20 ml of dry o-xylene. Tris(tert-butyl)phosphine (0.01 g) and tris(dibenzylideneacetone) dipalladium(0) (0.023 g) were dissolved in 10 ml of dry o-xylene and stirred for 10 minutes. The catalyst solution was added to the reaction mixture, stirred for 5 minutes and followed by sodium tert-butoxide (0.27 g, 2.83 mmol) and 25 ml of dry o-xylene. After another 10 minutes, the reaction flask was brought out of the drybox, attached to a nitrogen line and stirred at 75° C. overnight. Next day, reaction mixture was cooled to room temperature and filtered through a one-inch plug of silica gel and one inch of celite, washing with dichloromethane. Removal of volatiles under reduced pressure gave a solid which was triturated with diethyl ether. Yield 1.27 g (85.2%). Identity of the product was established by 1H NMR. The compound properties are given in Table 1.

Workup

  1. additionThe catalyst solution was added to the reaction mixture
  2. stirringstirred for 5 minutes
  3. waitAfter another 10 minutes
  4. stirringstirred at 75° C. overnight
  5. customNext day, reaction mixture
  6. filtrationfiltered through a one-inch plug of silica gel and one inch of celite
  7. washwashing with dichloromethane
  8. customRemoval of volatiles under reduced pressure
  9. customgave a solid which
  10. customwas triturated with diethyl ether

Sources & evidence

ORD record
ord-64c3c7291e024880bf335a26f248213d
Source dataset
uspto-grants-2015_03
Patent number
US08968883B2

Reaction notes

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