Aniline → Diisopropylaniline

HRID 578761Notes

Reaction equation

HRID 578761 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1>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]>[CH:2]([C:3]1[CH:4]=[CH:5][CH:6]=[C:7]([CH:5]([CH3:6])[CH3:4])[C:2]=1[NH2:1])([CH3:7])[CH3:3]

Participants

4

Reactant 1

HCID 6115Aniline

Product 1

HCID 32484Diisopropylaniline

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolvent

Procedure

The coupling reaction was carried out in toluene using Pd2(dba)3 as the catalyst precursor and the desired aniline at 90° C. overnight. After the reaction was completed the solution turned dark with an intense yellow coloration. Both compounds were isolated as yellow solids. 2-Ph-H was synthesized in good yield (76%), but when 2,6-diisopropylaniline was used to produce 2-Dipp-H, the yield decreased considerably (46%). Even over increased periods of time, no significant change in the yield was observed. This result is most likely a consequence of the steric hindrance afforded by the bulky 2,6-diisopropyl groups, diminishing the coordination of the amine to the palladium center. Neither 2-Ph-H nor 2-Dipp-H displayed fluorescence upon irradiation with UV light (254 nm). For 2-Dipp-H the 1H NMR displayed the characteristic resonance for the 2,6-diisopropyl groups and both ligands showed the amine proton shifted down field. The aromatic region of the 1H NMR spectrum was complicated by the overlap of some signals; nevertheless it was fully assigned using 2D experiments.

Workup

  1. customThe coupling reaction
  2. customat 90° C.
  3. customovernight
  4. customBoth compounds were isolated as yellow solids
  5. custom2-Ph-H was synthesized

Sources & evidence

ORD record
ord-09e71bfe304d47718c00e97a760b7335
Source dataset
uspto-grants-2015_05
Patent number
US09040704B2

Reaction notes

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