4-Bromotoluene → 4-[2-(4-Methylphenyl)ethenyl]-N,N-diphenylaniline

HRID 1178868Notes

Reaction equation

HRID 1178868 reaction equation
O(C(C)(C)C)[Na].[NH2:7][C:8]1[CH:15]=[CH:14][C:11]([CH:12]=[CH2:13])=[CH:10][CH:9]=1.Br[C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1.C1(N(C=[CH:37][C:38]2[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=2)C2C=CC=CC=2)C=CC=CC=1.Br[C:45]1[CH:50]=[CH:49][C:48](C)=[CH:47][CH:46]=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].C1(C)C=CC=CC=1>[C:17]1([N:7]([C:45]2[CH:50]=[CH:49][CH:48]=[CH:47][CH:46]=2)[C:8]2[CH:15]=[CH:14][C:11]([CH:12]=[CH:13][C:41]3[CH:40]=[CH:39][C:38]([CH3:37])=[CH:43][CH:42]=3)=[CH:10][CH:9]=2)[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1

Participants

8

Reactant 5

HCID 78054-BromotolueneHCID 7961BromobenzeneHCID 737004-AminostyreneHCID 53895446N-Phenyl-N-(2-phenylethenyl)anilineHCID 178418730sodium 2-methylpropan-2-olate

Product 1

HCID 540982294-[2-(4-Methylphenyl)ethenyl]-N,N-diphenylanilineYield 86%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolvent

Conditions

Temperature
60 °C

Procedure

An oven dried Schlenk tube equipped with a magnetic stirring bar was charged with Pd2dba3 (2 mol %) and NaO-t-Bu (3.5 mmol). The tube was capped with a rubber septum, evacuated and then flushed with argon three times. P(isoBuNCH2CH2)3N (4 mol %), 4-aminostyrene (1 mmol), bromobenzene (314 mg, 2 mmol) and toluene (10 mL) were successively added via syringe. After the tube was heated at 60° C. for 3 h, all the starting material was converted in to the N,N-diphenylaminostyrene as judged by TLC. To this reaction mixture, 4-bromotoluene (205 mg, 1.2 mmol) was added and the temperature was raised to 110° C. After heating for another 16 h, the reaction mixture was cooled to room temperature. The reaction mixture was filtered through a celite pad to remove the solid impurities and the filtrate was concentrated in vacuo. The crude product was purified by column chromatography using 1% EtOAc/hexane as eluants to afford the coupled product (6), namely N,N-diphenyl-4-[2-(4-methylphenyl) ethenyl]benzenamine (312 mg, 86%) as a yellow solid (See Entry 1 of Table 3).

Workup

  1. customAn oven dried Schlenk tube
  2. customequipped with a magnetic stirring bar
  3. customThe tube was capped with a rubber septum
  4. customevacuated
  5. customflushed with argon three times
  6. temperaturethe temperature was raised to 110° C
  7. temperatureAfter heating for another 16 h
  8. temperaturethe reaction mixture was cooled to room temperature
  9. filtrationThe reaction mixture was filtered through a celite pad
  10. customto remove the solid impurities
  11. concentrationthe filtrate was concentrated in vacuo
  12. customThe crude product was purified by column chromatography

Sources & evidence

ORD record
ord-77ccb3e0b8d24204b665a15b9488e47b
Source dataset
uspto-grants-2007_10
Patent number
US07276627B2

Reaction notes

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