Nitrogen → HCID 66874246, compound

HRID 921598Notes

Reaction equation

HRID 921598 reaction equation
[CH:1]1[C:13]2[N:12]([C:14]3[CH:15]=[C:16](Br)[CH:17]=[CH:18][CH:19]=3)[C:11]3[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=3)[C:5]=2[CH:4]=[CH:3][CH:2]=1.N#N.[NH2:23]C1C=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].O1CCOCC1>[CH:1]1[C:13]2[N:12]([C:14]3[CH:15]=[C:16]([CH:17]=[CH:18][CH:19]=3)[NH2:23])[C:11]3[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=3)[C:5]=2[CH:4]=[CH:3][CH:2]=1

Participants

6

Reactant 3

HCID 947NitrogenHCID 6115AnilineHCID 586908889-(3-Bromophenyl)-9H-carbazole

Product 1

HCID 66874246HCID 66874246, compoundYield 90%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 312751,4-DioxaneSolvent2×

Procedure

8.5 g 9-(3-bromophenyl)-carbazole from step (1b) above, 0.12 g Pd2DBA3 0.11 g dicyclohexylphosphinebiphenyl and 50 mL dioxane were stirred in a glove box (N2). 9.2 g LiN[Si(Me)3]2 and a further 10 mL dioxane were added and the reaction brought to reflux overnight. The reaction was cooled and remove from the glove and water was added slowly. The pH of the aqueous layer was brought to 9 with carbonate and then the mixture was extracted with DCM. The DCM layer was separated and dried over magnesium sulfate then chromatographed on silica eluting with 1:1 ethylacetate:hexanes. The product elutes as a tan solution which on evaporation and addition of methanol produces a tan colored crystalline solid in ˜90% yield. 1-H nmr shows it to be the desired aniline product.

Workup

  1. temperatureto reflux overnight
  2. temperatureThe reaction was cooled
  3. customremove from the glove and water
  4. additionwas added slowly
  5. extractionthe mixture was extracted with DCM
  6. customThe DCM layer was separated
  7. dry with materialdried over magnesium sulfate
  8. customthen chromatographed on silica eluting with 1:1 ethylacetate
  9. customThe product elutes as a tan solution which on evaporation and addition of methanol
  10. customproduces a tan colored crystalline solid in ˜90% yield

Sources & evidence

ORD record
ord-21ec0e8754984d639e9ecfc451dab049
Source dataset
uspto-grants-2016_03
Patent number
US09276217B2

Reaction notes

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