Carbazole → 3,6-Di-tert-butyl-9H-carbazole

HRID 1468465Notes

Reaction equation

HRID 1468465 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.Cl[C:15]([CH3:18])([CH3:17])[CH3:16]>[Cl-].[Cl-].[Zn+2].[N+](C)([O-])=O>[CH3:16][C:15]([C:3]1[CH:2]=[CH:1][C:13]2[NH:12][C:11]3[C:6]([C:5]=2[CH:4]=1)=[CH:7][C:8]([C:5]([CH3:6])([CH3:13])[CH3:4])=[CH:9][CH:10]=3)([CH3:18])[CH3:17]

Participants

5

Reactant 2

HCID 6854CarbazoleHCID 10486tert-BUTYL CHLORIDE3×

Product 1

HCID 154692093,6-Di-tert-butyl-9H-carbazole

Reagents, catalysts & solvents 2

HCID 3007855ZincchlorideCatalystHCID 6375NitromethaneSolvent

Procedure

To a 500 mL three-necked round bottom flask equipped with an over head stirrer, nitrogen gas bubbler, and an addition funnel add 20.02 g (120.8 mmol) of carbazole, 49.82 g (365.5 mmol) of ZnCl2, and 300 mL of nitromethane at room temperature. To the resulting dark brown slurry add 49.82 g (365.5 mmol) of 2-chloro-2-methylpropane (also known as tertiary-butyl chloride or t-BuCl) dropwise from the addition funnel over the period of 2.5 hours. After completing the addition, stir the resulting slurry for an additional 18 hours. Pour the reaction mixture into 800 mL of ice cold water, extract with 3×500 mL methylene chloride, combine and dry the extracts with anhydrous magnesium sulfate, filter, and concentrate the filtrate first by rotary evaporation and then by evaporation under high vacuum to remove nitromethane. Dissolve the resulting residue first in hot methylene chloride (70 mL) followed by hot hexanes (50 mL), allow the resulting solution to cool to room temperature and then placed it in a refrigerator overnight. Isolate the solids formed and wash the isolated solids with cold hexanes and then place them under high vacuum to yield 10.80 g (32.0%) of (P1) as off white crystals.

Workup

  1. customTo a 500 mL three-necked round bottom flask equipped with an over head stirrer
  2. customover the period of 2.5 hours
  3. additionthe addition
  4. extractionextract with 3×500 mL methylene chloride
  5. dry with materialdry the extracts with anhydrous magnesium sulfate
  6. filtrationfilter
  7. concentrationconcentrate the filtrate
  8. customfirst by rotary evaporation
  9. customby evaporation under high vacuum
  10. customto remove nitromethane
  11. dissolutionDissolve the resulting residue first in hot methylene chloride (70 mL)
  12. customin a refrigerator overnight
  13. customIsolate the solids
  14. customformed
  15. washwash the isolated solids with cold hexanes
  16. customto yield 10.80 g (32.0%) of (P1) as off white crystals

Sources & evidence

ORD record
ord-5d4bd264dfb9487ab7b767e814881c77
Source dataset
uspto-grants-2015_04
Patent number
US09000108B2

Reaction notes

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