5-Aminobenzene-1,3-dicarbonitrile → 3,5-Dicyanophenyl,3-(3,6-diphenyl-9-carbazolyl)phenylaniline

HRID 921603

Reaction equation

HRID 921603 reaction equation
C1([C:7]2[CH:8]=[CH:9][C:10]3[N:11]([C:26]4[CH:27]=[C:28](Br)[CH:29]=[CH:30][CH:31]=4)[C:12]4[C:17]([C:18]=3[CH:19]=2)=[CH:16][C:15]([C:20]2[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=2)=[CH:14][CH:13]=4)C=CC=CC=1.[NH2:33][C:34]1[CH:35]=[C:36]([C:42]#[N:43])[CH:37]=[C:38]([CH:41]=1)[C:39]#[N:40].[C:44](O[Na])([CH3:47])([CH3:46])C>C1(C)C=CC=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.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[C:42]([C:36]1[CH:35]=[C:34]([N:33]([C:8]2[CH:7]=[CH:19][CH:18]=[C:10]([N:11]3[C:12]4[CH:13]=[CH:14][C:15]([C:20]5[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=5)=[CH:16][C:17]=4[C:27]4[C:26]3=[CH:31][CH:30]=[C:29]([C:46]3[CH:44]=[CH:47][CH:17]=[CH:12][CH:13]=3)[CH:28]=4)[CH:9]=2)[C:7]2[CH:8]=[CH:9][CH:10]=[CH:18][CH:19]=2)[CH:41]=[C:38]([C:39]#[N:40])[CH:37]=1)#[N:43]

Participants

6

Reactant 3

HCID 197776195-Aminobenzene-1,3-dicarbonitrileHCID 581422319-(3-bromophenyl)-3,6-diphenyl-9H-CarbazoleHCID 178418730sodium 2-methylpropan-2-olate

Product 1

HCID 866960813,5-Dicyanophenyl,3-(3,6-diphenyl-9-carbazolyl)phenylanilineYield 50%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolvent

Procedure

9.0 g of carbazole from step (2b) from Example 2 above and 2.7 g 5-aminoisophthalonitrile were mixed in 50 mL toluene in nitrogen filled glove box. 0.2 g Pd2DBA3 and 0.09 g tri-t-butylphosphinewere added followed quickly by 1.81 g t-BuONa. The mixture was heated briefly to reflux then held at 80° C. overnight in the glove box with vigorous stirring. After cooling the reaction was chromatographed on silica using a gradient of DCM:hexanes (1:4 to 4:1) to elute the product which upon concentration and addition of hexanes precipitated the desired product in 50% yield (˜4 g) with structure confirmed by 1-H nmr spectroscopy.

Workup

  1. temperatureThe mixture was heated briefly
  2. temperatureto reflux
  3. temperatureAfter cooling the reaction
  4. customwas chromatographed on silica using a gradient of DCM:hexanes (1:4 to 4:1)
  5. washto elute the product which
  6. concentrationupon concentration and addition of hexanes
  7. customprecipitated the desired product in 50% yield (˜4 g) with structure

Sources & evidence

ORD record
ord-86c3656c5d0c45cf98468ef00c29196c
Source dataset
uspto-grants-2016_03
Patent number
US09276217B2

Linked notes

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