Toluene → 2-[6-(Dibenzothiophen-4-yl)dibenzothiophen-4-yl]dibenzo[f,h]quinoxaline

HRID 628242Notes

Reaction equation

HRID 628242 reaction equation
Cl[C:2]1[CH:11]=[N:10][C:9]2[C:4](=[C:5]3[CH:19]=[CH:18][CH:17]=[CH:16][C:6]3=[C:7]3[CH:15]=[CH:14][CH:13]=[CH:12][C:8]3=2)[N:3]=1.[C:20]1([C:36]2[C:44]3[C:43]4[CH:45]=[CH:46][CH:47]=[CH:48][C:42]=4[S:41][C:40]=3C=CC=2)[C:28]2[C:27]3[CH:29]=[CH:30][CH:31]=[C:32](B(O)O)[C:26]=3[S:25][C:24]=2[CH:23]=[CH:22][CH:21]=1.[C:49]1(C)[CH:54]=CC=C[CH:50]=1.C(=O)([O-])[O-].[K+].[K+]>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C(O)C>[CH:36]1[C:44]2[C:48]3[CH:47]=[CH:46][CH:45]=[CH:43][C:42]=3[S:41][C:40]=2[C:22]([C:23]2[C:24]3[S:25][C:26]4[C:32]([C:2]5[CH:11]=[N:10][C:9]6[C:4](=[C:5]7[CH:19]=[CH:18][CH:17]=[CH:16][C:6]7=[C:7]7[CH:15]=[CH:14][CH:13]=[CH:12][C:8]7=6)[N:3]=5)=[CH:31][CH:30]=[CH:29][C:27]=4[C:28]=3[CH:54]=[CH:49][CH:50]=2)=[CH:21][CH:20]=1

Participants

7

Reactant 4

HCID 1140TolueneHCID 11430Potassium CarbonateHCID 580194962-Chlorodibenzo[f,h]quinoxalineHCID 1317353434,4'-Bidibenzothiophene-6-boronic acid

Product 1

HCID 1179404122-[6-(Dibenzothiophen-4-yl)dibenzothiophen-4-yl]dibenzo[f,h]quinoxalineYield 41%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 702EthanolSolvent

Procedure

Into a 200-mL three-neck flask were put 1.6 g (6.1 mmol) of 2-chlorodibenzo[f,h]quinoxaline, 2.5 g (6.1 mmol) of 4,4′-bidibenzothiophene-6-boronic acid, and 0.19 g (0.62 mmol) of tris(2-methylphosphine)phosphine, and the air in the flask was replaced with nitrogen. To this mixture were added 20 mL of toluene, 10 mL of ethanol, and 6.0 mL of an aqueous solution of potassium carbonate (2.0 mol/L). This mixture was degassed by being stirred while the pressure was reduced. To this mixture, 70 mg (0.31 mmol) of palladium(II) acetate was added. This mixture was stirred at 80° C. under a nitrogen stream for 6 hours to precipitate a solid. The precipitated solid was collected by suction filtration. The collected solid was dissolved in approximately 6.0 L of hot toluene, and this solution was suction-filtered through Celite, alumina, and Florisil. The resulting filtrate was concentrated to give a solid. The solid was recrystallized by HPLC to give a white solid. The obtained solid was washed with hot toluene to give 1.5 g of white powder, which was an objective substance, in 41% yield. Synthesis Scheme (b-3) of Step 3 is shown below.

Workup

  1. customInto a 200-mL three-neck flask were put
  2. customThis mixture was degassed
  3. stirringThis mixture was stirred at 80° C. under a nitrogen stream for 6 hours
  4. customto precipitate a solid
  5. filtrationThe precipitated solid was collected by suction filtration
  6. dissolutionThe collected solid was dissolved in approximately 6.0 L of hot toluene
  7. filtrationthis solution was suction-filtered through Celite, alumina, and Florisil
  8. concentrationThe resulting filtrate was concentrated
  9. customto give a solid
  10. customThe solid was recrystallized by HPLC
  11. customto give a white solid
  12. washThe obtained solid was washed with hot toluene

Sources & evidence

ORD record
ord-3cd604a422e14644b8a6fde85f48cc13
Source dataset
uspto-grants-2016_04
Patent number
US09312498B2

Reaction notes

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