Potassium Carbonate → 3-(Dibenzothiophen-4-yl)-9H-carbazole

HRID 1189591Notes

Reaction equation

HRID 1189591 reaction equation
Br[C:2]1[CH:3]=[CH:4][C:5]2[NH:6][C:7]3[C:12]([C:13]=2[CH:14]=1)=[CH:11][CH:10]=[CH:9][CH:8]=3.[CH:15]1[C:23]2[C:22]3[CH:24]=[CH:25][CH:26]=[CH:27][C:21]=3[S:20][C:19]=2[C:18](B(O)O)=[CH:17][CH:16]=1.C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.C(=O)([O-])[O-].[K+].[K+]>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C(O)C.C1(C)C=CC=CC=1>[CH:15]1[C:23]2[C:22]3[CH:24]=[CH:25][CH:26]=[CH:27][C:21]=3[S:20][C:19]=2[C:18]([C:2]2[CH:3]=[CH:4][C:5]3[NH:6][C:7]4[C:12]([C:13]=3[CH:14]=2)=[CH:11][CH:10]=[CH:9][CH:8]=4)=[CH:17][CH:16]=1

Participants

8

Reactant 4

HCID 11430Potassium CarbonateHCID 80271Tri-o-tolylphosphineHCID 2524463-BromocarbazoleHCID 2734329Dibenzothiophene-4-boronic acid

Product 1

HCID 666918723-(Dibenzothiophen-4-yl)-9H-carbazoleYield 79%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 702EthanolSolventHCID 1140TolueneSolvent

Conditions

Temperature
80 °C

Procedure

Into a 200 mL three-neck flask were placed 3.0 g (12 mmol) of 3-bromocarbazole, 2.8 g (12 mmol) of dibenzothiophene-4-boronic acid, and 0.15 g (0.5 mol) of tri(ortho-tolyl)phosphine, and the air in the flask was replaced with nitrogen. To this mixture were added 40 mL of toluene, 40 mL of ethanol, and 15 mL (2.0 mol/L) of an aqueous solution of potassium carbonate. In the flask, the mixture was degassed by being stirred under reduced pressure. After the degassing, the air in the system was replaced with nitrogen, and 23 mg (0.10 mmol) of palladium(II) acetate was added to this mixture, and then the mixture was refluxed at 80° C. for 4 hours. After the reflux, the mixture was cooled to room temperature, whereby a solid was precipitated. About 100 mL of toluene was added to the mixture in which the solid was precipitated, and the resulting mixture was heated and stirred, so that the precipitated solid was dissolved. While kept hot, the obtained suspension was filtered through Celite (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 531-16855), Florisil (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 540-00135), and alumina. The solid obtained by concentration of the obtained filtrate was recrystallized from toluene, so that 3.4 g of a white solid which was the object of the synthesis was obtained in 79% yield. The reaction scheme of Step 1 is illustrated in the following scheme (a-1).

Workup

  1. customInto a 200 mL three-neck flask were placed
  2. customIn the flask, the mixture was degassed
  3. additionwas added to this mixture
  4. temperatureAfter the reflux, the mixture was cooled to room temperature
  5. customwhereby a solid was precipitated
  6. additionAbout 100 mL of toluene was added to the mixture in which the solid
  7. customwas precipitated
  8. temperaturethe resulting mixture was heated
  9. stirringstirred, so that the precipitated solid
  10. dissolutionwas dissolved
  11. filtrationthe obtained suspension was filtered through Celite (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 531-16855), Florisil (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 540-00135), and alumina
  12. customThe solid obtained by concentration of the obtained filtrate
  13. customwas recrystallized from toluene, so that 3.4 g of a white solid which
  14. customwas obtained in 79% yield
  15. customThe reaction scheme of Step 1

Sources & evidence

ORD record
ord-07cc4560184d4f26b62bede8be71b407
Source dataset
uspto-grants-2014_03
Patent number
US08674114B2

Reaction notes

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