Carbazole → 9-(3-Bromophenyl)-9H-carbazole

HRID 921597Notes

Reaction equation

HRID 921597 reaction equation
CC(C)([O-])C.[Na+].I[C:8]1[CH:9]=[C:10]([Br:14])[CH:11]=[CH:12][CH:13]=1.[CH:15]1[C:27]2[NH:26][C:25]3[C:20](=[CH:21][CH:22]=[CH:23][CH:24]=3)[C:19]=2[CH:18]=[CH:17][CH:16]=1>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.[Fe+2]>[CH:24]1[C:25]2[N:26]([C:8]3[CH:9]=[C:10]([Br:14])[CH:11]=[CH:12][CH:13]=3)[C:27]3[C:19](=[CH:18][CH:17]=[CH:16][CH:15]=3)[C:20]=2[CH:21]=[CH:22][CH:23]=1

Participants

6

Reactant 3

HCID 6854CarbazoleHCID 11561Benzene, 1-bromo-3-iodo-HCID 23676156Sodium t-butoxide

Product 1

HCID 586908889-(3-Bromophenyl)-9H-carbazole

Reagents, catalysts & solvents 2

HCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)CatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalyst

Procedure

Mix together 0.4 g Pd2DBA3 (DBA dibenzylideneacetone) and 0.4 g DPPF (DPPF 1,1′-bis(diphenylphosphino)ferrocene) and 4.3 g sodium t-butoxide and dissolve into 200 mL xylenes in glove box. Stir 15 mins then add 25 g of 3-iodo-bromobenzene. Stir 15 mins then add 5 g carbazole and the mix was brought to reflux. Reflux overnight using an air condensor in glove box. The solution immediately is dark purple/brown but on reaching ˜80 C. it is dark reddish brown and cloudy. After heating close to reflux overnight, the solution is dark brown and clear. Evaporated outside the glove box in rotovap and then dissolved in DCM and extracted (soxhlet) through a bed of silica and basic alumina (stacked in soxhlet) using DCM. Collect dark orange solution and evaporate to dryness. Leaves a dark orange oil. Wash with methanol and then dissolve into ether and reprecipitated with methanol—this product is slightly soluble in methanol.

Workup

  1. stirringStir 15 mins
  2. temperatureto reflux
  3. temperatureReflux overnight
  4. temperatureAfter heating
  5. customclose
  6. temperatureto reflux overnight
  7. customEvaporated outside the glove box in rotovap
  8. dissolutiondissolved in DCM
  9. extractionextracted (soxhlet) through a bed of silica and basic alumina (stacked in soxhlet)
  10. customCollect dark orange solution
  11. customevaporate to dryness
  12. customLeaves a dark orange oil
  13. washWash with methanol
  14. dissolutiondissolve into ether
  15. customreprecipitated with methanol—this product

Sources & evidence

ORD record
ord-9686b6184e1346799981a1dff4ebbc8b
Source dataset
uspto-grants-2016_03
Patent number
US09276217B2

Reaction notes

Loading…