Toluene → HCID 66691799, compound

HRID 2278680Notes

Reaction equation

HRID 2278680 reaction equation
Br[C:2]1[CH:3]=[CH:4][C:5]2[N:6]([C:16]3[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=3)[C:7]3[C:12]([C:13]=2[CH:14]=1)=[CH:11][C:10](Br)=[CH:9][CH:8]=3.[CH:22]1[C:30]2[C:29]3[CH:31]=[CH:32][CH:33]=[CH:34][C:28]=3[S:27][C:26]=2[C:25](B(O)O)=[CH:24][CH:23]=1.[C:38]1([CH3:44])[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=1.C(=O)([O-])[O-].[K+].[K+]>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.C(O)C>[CH:22]1[C:30]2[C:29]3[CH:31]=[CH:32][CH:33]=[CH:34][C:28]=3[S:27][C:26]=2[C:25]([C:2]2[CH:3]=[CH:4][C:5]3[N:6]([C:16]4[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=4)[C:7]4[C:12]([C:13]=3[CH:14]=2)=[CH:11][C:10]([C:42]2[C:43]3[S:27][C:26]5[CH:25]=[CH:24][CH:23]=[CH:22][C:44]=5[C:38]=3[CH:39]=[CH:40][CH:41]=2)=[CH:9][CH:8]=4)=[CH:24][CH:23]=1

Participants

8

Reactant 4

HCID 1140TolueneHCID 11430Potassium CarbonateHCID 2734329Dibenzothiophene-4-boronic acidHCID 110257913,6-Dibromo-9-phenylcarbazole

Product 1

HCID 66691799HCID 66691799, compoundYield 47%

Reagents, catalysts & solvents 3

HCID 80271Tri-o-tolylphosphineCatalystHCID 167845palladium(II) acetateCatalystHCID 702EthanolSolvent

Procedure

To a 200-mL three-neck flask were added 2.0 g (5.0 mmol) of 3,6-dibromo-9-phenyl-9H-carbazole, 3.2 g (11 mmol) of dibenzothiophene-4-boronic acid, 10 mg (0.1 mmol) of palladium(II) acetate, 30 mg (0.1 mmol) of tri(ortho-tolyl)phosphine, 50 mL of toluene, 5 mL of ethanol, and 7.5 mL of a 2 mol/L aqueous potassium carbonate solution. This mixture was degassed while being stirred under reduced pressure, and then heated and stirred at 90° C. for 6 hours in a nitrogen atmosphere to be reacted. After the reaction, this reaction mixture solution was cooled to room temperature, and then filtered to give a residue while being washed with water, ethanol, toluene, and hexane in this order. The residue was purified by silica gel column chromatography (a developing solvent in which the toluene/hexane ratio was 1:3). The fraction thus obtained was concentrated, acetone and ethanol were added thereto, and the mixture was irradiated with ultrasonic waves. Then, recrystallization gave 1.4 g of a white powder in 47% yield. The synthesis scheme of Step 1 is shown in (A-1).

Workup

  1. customThis mixture was degassed
  2. temperatureheated
  3. stirringstirred at 90° C. for 6 hours in a nitrogen atmosphere
  4. customto be reacted
  5. customAfter the reaction
  6. filtrationfiltered
  7. customto give a residue
  8. washwhile being washed with water, ethanol, toluene, and hexane in this order
  9. customThe residue was purified by silica gel column chromatography (a developing solvent in which the toluene/hexane ratio
  10. customThe fraction thus obtained
  11. concentrationwas concentrated
  12. additionacetone and ethanol were added
  13. customthe mixture was irradiated with ultrasonic waves
  14. customThen, recrystallization

Sources & evidence

ORD record
ord-da0b69951f5d41e6993827937836d784
Source dataset
uspto-grants-2015_09
Patent number
US09133173B2

Reaction notes

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