Carbazole → 9H-Carbazole-1-carbonitrile

HRID 623248Notes

Reaction equation

HRID 623248 reaction equation
B(Cl)(Cl)Cl.[CH:5]1[C:17]2[NH:16][C:15]3[C:10](=[CH:11][CH:12]=[CH:13][CH:14]=3)[C:9]=2[CH:8]=[CH:7][CH:6]=1.CS[C:20]#[N:21].[OH-].[Na+]>C1(C)C=CC=CC=1>[C:20]([C:14]1[C:15]2[NH:16][C:17]3[C:9](=[CH:8][CH:7]=[CH:6][CH:5]=3)[C:10]=2[CH:11]=[CH:12][CH:13]=1)#[N:21]

Participants

6

Reactant 4

HCID 6854CarbazoleHCID 11168Methyl thiocyanateHCID 14798Sodium HydroxideHCID 25135Boron Trichloride

Product 1

HCID 138631989H-Carbazole-1-carbonitrileYield 75%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent2×

Procedure

To 5.4 ml of a solution of 2.04M of boron trichloride in toluene was added a solution of 1.67 g of carbazole in 10 ml of toluene, and the mixture was refluxed for 1 hr. After cooling, the mixture was treated with 1 ml of methyl thiocyanate and stirred at room temperature for 3 hr. The reaction mixture was poured into 4N aqueous sodium hydroxide under ice-cooling and stirred at 100° C. on an oil bath for 30 min. After cooling, the reaction solution was extracted with methylene chloride, washed with water and dried over anhydrous magnesium sulfate. The residue was chromatographed on a column of silica gel, and the eluate with methylene chloride was discarded. The eluate with 10% acetonitrile-methylene chloride was concentrated, and the product was recrystallized from acetone-ether to give 1.45 g of 1-cyanocarbazole as white crystals melting at 200°-201° C.

Workup

  1. temperaturethe mixture was refluxed for 1 hr
  2. temperatureAfter cooling
  3. temperaturecooling
  4. stirringstirred at 100° C. on an oil bath for 30 min
  5. temperatureAfter cooling
  6. extractionthe reaction solution was extracted with methylene chloride
  7. washwashed with water
  8. dry with materialdried over anhydrous magnesium sulfate
  9. customThe residue was chromatographed on a column of silica gel
  10. concentrationThe eluate with 10% acetonitrile-methylene chloride was concentrated
  11. customthe product was recrystallized from acetone-ether

Sources & evidence

ORD record
ord-d1e9bf383cb44af58c0c5606de4f61e3
Source dataset
uspto-grants-1988_09
Patent number
US04774331

Reaction notes

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