Tris(1,1-dimethylethyl)phosphine → 7-Bromo-10-[3-(4,6-diphenylpyrimidin-2-yl)phenyl]-12,12-dimethyl-10,12-dihydro-10-azaindeno[2,1-b]fluorene

HRID 634553Notes

Reaction equation

HRID 634553 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]2[C:12](=[CH:13][CH:14]=1)[NH:11][C:10]1[CH:9]=[C:8]3[C:15]([CH3:23])([CH3:22])[C:16]4[C:21]([C:7]3=[CH:6][C:5]2=1)=[CH:20][CH:19]=[CH:18][CH:17]=4.Br[C:25]1[CH:26]=[C:27]([C:31]2[N:36]=[C:35]([C:37]3[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=3)[CH:34]=[C:33]([C:43]3[CH:48]=[CH:47][CH:46]=[CH:45][CH:44]=3)[N:32]=2)[CH:28]=[CH:29][CH:30]=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]>[Br:1][C:2]1[CH:3]=[C:4]2[C:12](=[CH:13][CH:14]=1)[N:11]([C:29]1[CH:30]=[CH:25][CH:26]=[C:27]([C:31]3[N:36]=[C:35]([C:37]4[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=4)[CH:34]=[C:33]([C:43]4[CH:48]=[CH:47][CH:46]=[CH:45][CH:44]=4)[N:32]=3)[CH:28]=1)[C:10]1[CH:9]=[C:8]3[C:15]([CH3:23])([CH3:22])[C:16]4[C:21]([C:7]3=[CH:6][C:5]2=1)=[CH:20][CH:19]=[CH:18][CH:17]=4

Participants

7

Reactant 4

HCID 83681Tris(1,1-dimethylethyl)phosphineHCID 23676156Sodium t-butoxideHCID 589431812-(3-Bromophenyl)-4,6-diphenylpyrimidineHCID 667977897-Bromo-12,12-dimethyl-10,12-dihydro-10-azaindeno[2,1-b]fluorene

Product 1

HCID 679505077-Bromo-10-[3-(4,6-diphenylpyrimidin-2-yl)phenyl]-12,12-dimethyl-10,12-dihydro-10-azaindeno[2,1-b]fluorene

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 7809P-XyleneSolvent

Procedure

19.55 g (53.97 mmol) of 7-bromo-12,12-dimethyl-10,12-dihydro-10-aza-indeno[2,1-b]fluorene 19, 22.99 g (59.37 mmol) of 2-(3-bromophenyl)-4,6-diphenylpyrimidine 14 and 15.84 g (164.81 mmol) of NaOtBu are suspended in 820 ml of p-xylene. 245.0 mg (1.09 mmol) of Pd(OAc)2 and 3.3 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 tolu-ene, recrystallised from toluene. The yield is 21.65 g (65%).

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 tolu-ene
  8. customrecrystallised from toluene

Sources & evidence

ORD record
ord-a820d08c3110430f8e7825a215a7ffdd
Source dataset
uspto-grants-2016_04
Patent number
US09324954B2

Reaction notes

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