Tris(1,1-dimethylethyl)phosphine → 7-{9-[3-(4,6-Diphenylpyrimidin-2-yl)phenyl]-9H-carbazol-3-yl}-12,12-dimethyl-10-phenyl-10,12-dihydro-10-azaindeno[2,1-b]fluorene

HRID 634555Notes

Reaction equation

HRID 634555 reaction equation
[CH:1]1[C:13]2[NH:12][C:11]3[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=3)[C:5]=2[CH:4]=[C:3]([C:14]2[CH:15]=[C:16]3[C:24](=[CH:25][CH:26]=2)[N:23]([C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=2)[C:22]2[CH:21]=[C:20]4[C:33]([CH3:41])([CH3:40])[C:34]5[C:39]([C:19]4=[CH:18][C:17]3=2)=[CH:38][CH:37]=[CH:36][CH:35]=5)[CH:2]=1.Br[C:43]1[CH:44]=[C:45]([C:49]2[N:54]=[C:53]([C:55]3[CH:60]=[CH:59][CH:58]=[CH:57][CH:56]=3)[CH:52]=[C:51]([C:61]3[CH:66]=[CH:65][CH:64]=[CH:63][CH:62]=3)[N:50]=2)[CH:46]=[CH:47][CH:48]=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]>[C:61]1([C:51]2[CH:52]=[C:53]([C:55]3[CH:60]=[CH:59][CH:58]=[CH:57][CH:56]=3)[N:54]=[C:49]([C:45]3[CH:46]=[C:47]([N:12]4[C:13]5[CH:1]=[CH:2][C:3]([C:14]6[CH:15]=[C:16]7[C:24](=[CH:25][CH:26]=6)[N:23]([C:27]6[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=6)[C:22]6[CH:21]=[C:20]8[C:33]([CH3:41])([CH3:40])[C:34]9[C:39]([C:19]8=[CH:18][C:17]7=6)=[CH:38][CH:37]=[CH:36][CH:35]=9)=[CH:4][C:5]=5[C:6]5[C:11]4=[CH:10][CH:9]=[CH:8][CH:7]=5)[CH:48]=[CH:43][CH:44]=3)[N:50]=2)[CH:66]=[CH:65][CH:64]=[CH:63][CH:62]=1

Participants

7

Reactant 4

HCID 83681Tris(1,1-dimethylethyl)phosphineHCID 23676156Sodium t-butoxideHCID 589431812-(3-Bromophenyl)-4,6-diphenylpyrimidineHCID 676095847-(9H-Carbazol-3-yl)-12,12-dimethyl-10-phenyl-10,12-dihydro-10-azaindeno[2,1-b]fluorene

Product 1

HCID 679505147-{9-[3-(4,6-Diphenylpyrimidin-2-yl)phenyl]-9H-carbazol-3-yl}-12,12-dimethyl-10-phenyl-10,12-dihydro-10-azaindeno[2,1-b]fluorene

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 7809P-XyleneSolvent

Procedure

19.50 g (37.17 mmol) of 7-(9H-carbazol-3-yl)-12,12-dimethyl-10-phenyl-10,12-dihydro-10-azaindeno[2,1-b]fluorene 23, 15.83 g (40.88 mmol) of 2-(3-bromophenyl)-4,6-diphenylpyrimidine 14 and 10.91 g (113.50 mmol) of NaOtBu are suspended in 600 ml of p-xylene. 168.73 mg (0.75 mmol) of Pd(OAc)2 and 2.3 ml of a 1M tri-tert-butylphosphine solution are added to this suspension. The reaction mixture is heated under reflux for 19 h. After cooling, the organic phase is separated off, washed three times with 100 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 yield is 15.44 g (50%).

Workup

  1. temperatureThe reaction mixture is heated
  2. temperatureunder reflux for 19 h
  3. temperatureAfter cooling
  4. customthe organic phase is separated off
  5. washwashed three times with 100 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-c097768cc0b241359cbf8bd88ff498c2
Source dataset
uspto-grants-2016_04
Patent number
US09324954B2

Reaction notes

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