Tris(1,1-dimethylethyl)phosphine → 12,12-Dimethyl-10-[1,1';3',1'']terphenyl-5'-yl-10,12-dihydro-10-azaindeno[2,1-b]fluorene

HRID 2275931Notes

Reaction equation

HRID 2275931 reaction equation
[CH3:1][C:2]1([CH3:22])[C:10]2=[CH:11][C:12]3[NH:13][C:14]4[C:19]([C:20]=3[CH:21]=[C:9]2[C:8]2[C:3]1=[CH:4][CH:5]=[CH:6][CH:7]=2)=[CH:18][CH:17]=[CH:16][CH:15]=4.Br[C:24]1[CH:25]=[C:26]([C:36]2[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=2)[CH:27]=[C:28]([C:30]2[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=2)[CH:29]=1.CC([O-])(C)C.[Na+].C(P(C(C)(C)C)C(C)(C)C)(C)(C)C>CC1C=CC(C)=CC=1.CC([O-])=O.CC([O-])=O.[Pd+2]>[CH3:1][C:2]1([CH3:22])[C:10]2=[CH:11][C:12]3[N:13]([C:24]4[CH:29]=[C:28]([C:30]5[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=5)[CH:27]=[C:26]([C:36]5[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=5)[CH:25]=4)[C:14]4[C:19]([C:20]=3[CH:21]=[C:9]2[C:8]2[C:3]1=[CH:4][CH:5]=[CH:6][CH:7]=2)=[CH:18][CH:17]=[CH:16][CH:15]=4

Participants

7

Reactant 4

HCID 83681Tris(1,1-dimethylethyl)phosphineHCID 100702575'-Bromo-1,1':3',1''-terphenylHCID 23676156Sodium t-butoxideHCID 665852047,7-Dimethyl-5,7-dihydroindeno[2,1-b]carbazole

Product 1

HCID 6679766212,12-Dimethyl-10-[1,1';3',1'']terphenyl-5'-yl-10,12-dihydro-10-azaindeno[2,1-b]fluorene

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 7809P-XyleneSolvent

Procedure

30 g (106 mmol) of 12,12-dimethyl-10,12-dihydro-10-azaindeno[2,1-b]fluorene, 13.3 g (114 mmol) of 5′-bromo-[1,1′;3′,1″]terphenyl and 30.5 g of NaOtBu are suspended in 1.5 l of p-xylene. 0.5 g (2.11 mmol) of Pd(OAc)2 and 1.6 ml of a 1 M tri-tert-butylphosphine solution are added to this suspension. The reaction mixture is heated under reflux for 16 h. After cooling, the organic phase is separated off, washed three times with 200 ml of water and subsequently evaporated to dryness. The residue is extracted with hot toluene, recrystallised from toluene and finally sublimed in a high vacuum, the purity is 99.9%. The yield is 15.8 g (31 mmol, 72%).

Workup

  1. temperatureThe reaction mixture is heated
  2. temperatureunder reflux for 16 h
  3. temperatureAfter cooling
  4. customthe organic phase is separated off
  5. washwashed three times with 200 ml of water
  6. customsubsequently evaporated to dryness
  7. extractionThe residue is extracted with hot toluene
  8. customrecrystallised from toluene

Sources & evidence

ORD record
ord-c7b1398bf89d47c7be91646677b0a4da
Source dataset
uspto-grants-2015_09
Patent number
US09126970B2

Reaction notes

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