1,1'-Biphenyl-4-yl-boronic acid → 2,2',4,4',7,7'-Hexabiphenylyl-9,9'-spirobifluorene

HRID 1633819Notes

Reaction equation

HRID 1633819 reaction equation
Br[C:2]1[CH:14]=[C:13]2[C:5]([C:6]3[C:11](=[CH:12]2)[C:10]2([C:26]4[C:18]([C:19]5[C:24]([CH:25]=4)=[CH:23][CH:22]=[CH:21][CH:20]=5)=[CH:17][CH:16]=[CH:15]2)[C:9](Br)=[C:8](Br)[C:7]=3Br)=[C:4](Br)[C:3]=1Br.B(O)(O)[C:33]1[CH:34]=[CH:35][C:36]([C:39]2[CH:40]=[CH:41][CH:42]=[CH:43][CH:44]=2)=[CH:37][CH:38]=1>C1(C)C=CC=CC=1.C(=O)([O-])[O-].[K+].[K+].C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[C:36]1([C:39]2[CH:40]=[CH:41][CH:42]=[CH:43][CH:44]=2)[CH:35]=[CH:34][CH:33]=[CH:38][C:37]=1[C:2]1[CH:14]=[C:13]([C:12]2[CH:25]=[CH:26][CH:18]=[CH:17][C:11]=2[C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)[C:5]2[C:6]3[C:15](=[CH:10][C:9]([C:40]4[CH:41]=[CH:42][CH:43]=[CH:44][C:39]=4[C:36]4[CH:37]=[CH:38][CH:33]=[CH:34][CH:35]=4)=[CH:8][CH:7]=3)[C:16]3([C:17]4[CH:18]=[C:26]([C:40]5[CH:41]=[CH:42][CH:43]=[CH:44][C:39]=5[C:36]5[CH:37]=[CH:38][CH:33]=[CH:34][CH:35]=5)[CH:25]=[C:24]([C:23]5[CH:22]=[CH:21][CH:20]=[CH:16][C:15]=5[C:10]5[CH:11]=[CH:6][CH:7]=[CH:8][CH:9]=5)[C:19]=4[C:42]4[C:41]3=[CH:40][C:39]([C:36]3[CH:37]=[CH:38][CH:33]=[CH:34][C:35]=3[C:13]3[CH:14]=[CH:2][CH:3]=[CH:4][CH:5]=3)=[CH:44][CH:43]=4)[C:4]=2[CH:3]=1

Participants

6

Reactant 2

HCID 1512531,1'-Biphenyl-4-yl-boronic acidHCID 86753354Hexabromospirobifluorene

Product 1

HCID 220160562,2',4,4',7,7'-Hexabiphenylyl-9,9'-spirobifluorene

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 1140TolueneSolvent2×HCID 11430Potassium CarbonateSolvent

Procedure

1.6 g of hexabromospirobifluorene and 3 g of biphenylboronic acid were suspended in a mixture of 50 ml of toluene and 50 ml of 1 M potassium carbonate solution in a 250 ml two-necked flask with a reflux condenser and precision glass stirrer. The mixture was boiled under reflux under nitrogen, and 115 mg of tetrakis(triphenylphosphine)palladium in 5 ml of toluene were added. The mixture was boiled under reflux for 7 hours, while stirring. When the reaction had ended, the cooled solution was filtered off and the filtrate was extracted 2× by shaking with water (chloroform was added for better phase separation). The organic phase was dried over sodium sulfate and filtered over a short column with silica gel and the solvent was then stripped off on a rotary evaporator. For further purification, the product was recrystallized from methylene chloride/pentane. 2 g (80%) of colorless crystals which fluoresce blue under UV illumination were obtained.

Workup

  1. temperatureunder reflux under nitrogen
  2. temperatureunder reflux for 7 hours
  3. filtrationthe cooled solution was filtered off
  4. extractionthe filtrate was extracted 2×
  5. stirringby shaking with water (chloroform
  6. additionwas added for better phase separation)
  7. dry with materialThe organic phase was dried over sodium sulfate
  8. filtrationfiltered over a short column with silica gel
  9. customthe solvent was then stripped off on a rotary evaporator
  10. customFor further purification
  11. customthe product was recrystallized from methylene chloride/pentane
  12. customwere obtained

Sources & evidence

ORD record
ord-1c024e0c201a4d7bbbd02dcd30a20702
Source dataset
uspto-grants-2003_01
Patent number
US06504042B1

Reaction notes

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