Carbazole → 1-Phenyl-9H-carbazole

HRID 2283157Notes

Reaction equation

HRID 2283157 reaction equation
[CH:1]1[C:13]2[NH:12][C:11]3[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=3)[C:5]=2[CH:4]=[CH:3][CH:2]=1.I[C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1.C(O[Na])(C)(C)C>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1(C)C(C)=CC=CC=1>[C:15]1([C:10]2[C:11]3[NH:12][C:13]4[C:5](=[CH:4][CH:3]=[CH:2][CH:1]=4)[C:6]=3[CH:7]=[CH:8][CH:9]=2)[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1

Participants

6

Reactant 3

HCID 6854CarbazoleHCID 11575IodobenzeneHCID 178418730sodium 2-methylpropan-2-olate

Product 1

HCID 134974741-Phenyl-9H-carbazoleYield 84.1%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 7237O-XyleneSolvent

Procedure

Ina stream of argon, 670 g of carbazole, 850 kg of iodobenzene, 20 L of xylene, 460 g of t-BuONa, and palladium acetate (Pd(OAc)2) were added, and then the mixture was refluxed for 8 hours. Impurities were filtrated, and then the filtrate was concentrated under reduced pressure and washed with hexane. After that, the washed product was dried. As a result, 820 g of phenylcarbazole were obtained as a white powder. In a stream of argon, 24 g of phenylcarbazole, 8.3 g of potassium iodide, 10.7 g of potassium iodate, 500 mL of ethanol, and 8 mL of sulfuric acid were added into a 1,000-mL three-necked flask, and then the mixture was stirred at 75° C. for 2 hours. After that, the reaction product was injected into ice water, and then the mixture was extracted with ethyl acetate and water. After having been washed with water, the extract was subjected to column chromatography with silica gel. As a result, 67 g of a white powder were obtained. A reaction was performed in the same manner as in the synthesis of Intermediate 1 except that 9-phenylcarbazole was used instead of 4-bromobiphenyl. As a result, 22.3 g of a white powder were obtained. FD-MS analysis identified the powder as Intermediate 11.

Workup

  1. temperaturethe mixture was refluxed for 8 hours
  2. filtrationImpurities were filtrated
  3. concentrationthe filtrate was concentrated under reduced pressure
  4. washwashed with hexane
  5. customAfter that, the washed product was dried

Sources & evidence

ORD record
ord-0621cbca20fe413b8259af4cea26ecef
Source dataset
uspto-grants-2015_09
Patent number
US09145363B2

Reaction notes

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