Aniline → N,9-Diphenyl-9H-carbazol-3-amine

HRID 1916013Notes

Reaction equation

HRID 1916013 reaction equation
Br[C:2]1[CH:3]=[CH:4][C:5]2[N:6]([C:15]3[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=3)[C:7]3[C:12]([C:13]=2[CH:14]=1)=[CH:11][CH:10]=[CH:9][CH:8]=3.CC(C)([O-])C.[Na+].C1(C)C(C)=CC=CC=1.[NH2:35][C:36]1[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=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].[CH-]1C(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=C1.[CH-]1C(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=C1.[Fe+2].C1(C)C=CC=CC=1>[C:36]1([NH:35][C:2]2[CH:3]=[CH:4][C:5]3[N:6]([C:15]4[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=4)[C:7]4[C:12]([C:13]=3[CH:14]=2)=[CH:11][CH:10]=[CH:9][CH:8]=4)[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=1

Participants

8

Reactant 4

HCID 6115AnilineHCID 7237O-XyleneHCID 189426243-Bromo-9-phenylcarbazoleHCID 23676156Sodium t-butoxide

Product 1

HCID 59815954N,9-Diphenyl-9H-carbazol-3-amineYield 75%

Reagents, catalysts & solvents 3

HCID 6505921(1E,4E)-1,5-diphenylpenta-1,4-dien-3-one; palladiumCatalystHCID 152416121,1`-Bis(diphenylphosphino)ferroceneCatalystHCID 1140TolueneSolvent

Conditions

Temperature
90 °C

Procedure

Into a 500 mL three-neck flask were added 19 g (60 mmol) of 3-bromo-9-phenylcarbazole, 0.34 g (0.60 mmol) of bis(dibenzylideneacetone)palladium(0), 1.6 g (3.0 mmol) of 1,1-bis(diphenylphosphino)ferrocene, and 13 g (0.18 mol) of sodium tert-butoxide, and the atmosphere in the flask was substituted with nitrogen. Then, 110 mL of dehydrated xylene and 7.0 g (75 mmol) of aniline were added thereto. This was heated and stirred at 90° C. for 7.5 hours under a stream of nitrogen. After the reaction was completed, about 500 mL of hot toluene was added to the reaction solution, followed by filtration through Florisil (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 540-00135), alumina, and Celite (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 531-16855). The obtained filtrate was concentrated, and hexane and ethyl acetate were added thereto, followed by irradiation with ultrasonic waves, whereby a solid substance was precipitated. This solid substance was collected by suction filtration and dried to produce 15 g (75% yield) of N-phenyl-(9-phenyl-9H-carbazol-3-yl)amine (abbreviation: PCA) as a milky white powder. By a nuclear magnetic resonance method (NMR), this compound was proved to be N-phenyl-(9-phenyl-9H-carbazol-3-yl)amine (abbreviation: PCA).

Workup

  1. temperatureThis was heated
  2. filtrationfollowed by filtration through Florisil (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 540-00135), alumina, and Celite (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 531-16855)
  3. concentrationThe obtained filtrate was concentrated
  4. additionhexane and ethyl acetate were added
  5. customfollowed by irradiation with ultrasonic waves, whereby a solid substance
  6. customwas precipitated
  7. filtrationThis solid substance was collected by suction filtration
  8. customdried

Sources & evidence

ORD record
ord-f1f78de8b4b74da191ce7f4112ac6977
Source dataset
uspto-grants-2013_12
Patent number
US08617725B2

Reaction notes

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