Carbazole → 4-(9H-Carbazol-9-yl)aniline

HRID 1895847Notes

Reaction equation

HRID 1895847 reaction equation
I[C:2]1[CH:7]=[CH:6][C:5]([NH2:8])=[CH:4][CH:3]=1.[CH:9]1[C:21]2[NH:20][C:19]3[C:14](=[CH:15][CH:16]=[CH:17][CH:18]=3)[C:13]=2[CH:12]=[CH:11][CH:10]=1>O(C1C=CC=CC=1)C1C=CC=CC=1.[Cu-]=O>[CH:18]1[C:19]2[N:20]([C:2]3[CH:7]=[CH:6][C:5]([NH2:8])=[CH:4][CH:3]=3)[C:21]3[C:13](=[CH:12][CH:11]=[CH:10][CH:9]=3)[C:14]=2[CH:15]=[CH:16][CH:17]=1

Participants

5

Reactant 2

HCID 6854CarbazoleHCID 108934-Iodoaniline

Product 1

HCID 6210474-(9H-Carbazol-9-yl)aniline

Reagents, catalysts & solvents 2

HCID 178419072HCID 178419072, compoundCatalystHCID 7583Diphenyl EtherSolvent

Conditions

Temperature
190 °C

Procedure

4-(9H-carbazol-9-yl)benzenamine (A) was prepared through the Ullmann Reaction following the procedures reported in the literature (Macromolecules 2004, 37, 5531-5537). A mixture of 4-iodobenzenamine (2.19 g, 10 mmol), copper (I) oxide (2.18 g, 20 mmol) and carbazole (3.35 g, 20 mmol) in 40 ml 1-phenoxybenzene was heated to 190° C. in an oil bath for 24 h under N2 atmosphere. The reaction mixture was cooled to room temperature and then filtered by fast silica gel column to remove excess copper complex and 1-phenoxybenzene. The filtrate was evaporated to dryness and passed through a silica gel column using hexane and ethyl acetate mixture (6:1) as eluent to give product, yielding 2.37 g (92%). 1H NMR (400 MHz, CDCl3): δ(ppm) 8.164-8.144 (d, J=8.0 Hz, 2H), 7.432-7.395 (t, J=8.0 Hz, 2H), 7.353-7.277 (m, 6H), 6.912-6.891 (d, J=7.6 Hz, 2H), 4.019 (w, 2H).

Workup

  1. temperatureThe reaction mixture was cooled to room temperature
  2. filtrationfiltered by fast silica gel column
  3. customto remove excess copper complex and 1-phenoxybenzene
  4. customThe filtrate was evaporated to dryness
  5. customto give product
  6. customyielding 2.37 g (92%)

Sources & evidence

ORD record
ord-29e679733c624d9ea5be3eeafa7bce08
Source dataset
uspto-grants-2013_08
Patent number
US08518559B2

Reaction notes

Loading…