Potassium Carbonate → Bidibenzo[b,d]thiophene

HRID 628240Notes

Reaction equation

HRID 628240 reaction equation
I[C:2]1[C:7]2[S:8][C:9]3[CH:14]=[CH:13][CH:12]=[CH:11][C:10]=3[C:6]=2[CH:5]=[CH:4][CH:3]=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](B(O)O)=[CH:17][CH:16]=1.C(=O)([O-])[O-].[K+].[K+].[O-][Si]([O-])=O.[Mg+2]>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.CC1C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.C(O)C.C1(C)C=CC=CC=1>[C:5]1([C:15]2[C:23]3[C:22]4[CH:24]=[CH:25][CH:26]=[CH:27][C:21]=4[S:20][C:19]=3[CH:18]=[CH:17][CH:16]=2)[C:6]2[C:10]3[CH:11]=[CH:12][CH:13]=[CH:14][C:9]=3[S:8][C:7]=2[CH:2]=[CH:3][CH:4]=1

Participants

9

Reactant 4

HCID 11430Potassium CarbonateHCID 61680MAGNESIUM SILICATE (synthetic)HCID 4583534-IododibenzothiopheneHCID 2734329Dibenzothiophene-4-boronic acid

Product 1

HCID 85728735Bidibenzo[b,d]thiopheneYield 90%

Reagents, catalysts & solvents 4

HCID 80271Tri-o-tolylphosphineCatalystHCID 167845palladium(II) acetateCatalystHCID 702EthanolSolventHCID 1140TolueneSolvent

Procedure

Into a 500-mL three-neck flask were put 4.7 g (15 mmol) of 4-iododibenzothiophene, 3.6 g (16 mmol) of dibenzothiophene-4-boronic acid, and 91 mg (0.30 mmol) of tris(2-methylphenyl)phosphine, and the air in the flask was replaced with nitrogen. To this mixture were added 50 mL of toluene, 25 mL of ethanol, and 15 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, 34 mg (0.15 mmol) of palladium(II) acetate was added. This mixture was stirred at 80° C. under a nitrogen stream for 3 hours to precipitate a solid. The precipitated solid was collected by suction filtration. The aqueous layer of the obtained filtrate was subjected to extraction with toluene, and the extracted solution and the organic layer were combined and washed with saturated brine. The organic layer was dried with magnesium sulfate, and this mixture was gravity-filtered. A solid obtained by concentrating the resulting filtrate and the solid collected by suction filtration were dissolved in approximately 100 mL of toluene. This solution was suction-filtered through Celite (Catalog No. 531-16855, produced by Wako Pure Chemical Industries, Ltd.), alumina, and Florisil (Catalog No. 540-00135, produced by Wako Pure Chemical Industries, Ltd). A solid obtained by concentrating the resulting filtrate was recrystallized from toluene/hexane to give 4.9 g of a white solid, which was an objective substance, in 90% yield. Synthesis Scheme (a-1) of Step 1 is shown below.

Workup

  1. customInto a 500-mL three-neck flask were put
  2. customThis mixture was degassed
  3. stirringThis mixture was stirred at 80° C. under a nitrogen stream for 3 hours
  4. customto precipitate a solid
  5. filtrationThe precipitated solid was collected by suction filtration
  6. extractionThe aqueous layer of the obtained filtrate was subjected to extraction with toluene
  7. washwashed with saturated brine
  8. dry with materialThe organic layer was dried with magnesium sulfate
  9. filtrationthis mixture was gravity-filtered
  10. customA solid obtained
  11. concentrationby concentrating the resulting filtrate
  12. filtrationthe solid collected by suction filtration
  13. dissolutionwere dissolved in approximately 100 mL of toluene
  14. filtrationThis solution was suction-filtered through Celite (Catalog No
  15. custom531-16855, produced by Wako Pure Chemical Industries, Ltd
  16. custom540-00135, produced by Wako Pure Chemical Industries, Ltd)
  17. customA solid obtained
  18. concentrationby concentrating the resulting filtrate
  19. customwas recrystallized from toluene/hexane

Sources & evidence

ORD record
ord-e176c0c4aed4417289812eeafe49e87e
Source dataset
uspto-grants-2016_04
Patent number
US09312498B2

Reaction notes

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