Phenyl-1-naphthylamine → N-(4-Bromophenyl)-N-phenyl-1-naphthylamine

HRID 516487

Reaction equation

HRID 516487 reaction equation
[C:1]1([NH:7][C:8]2[C:17]3[C:12](=[CH:13][CH:14]=[CH:15][CH:16]=3)[CH:11]=[CH:10][CH:9]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[Br:18][C:19]1[CH:24]=[CH:23][C:22](I)=[CH:21][CH:20]=1.C(P(C(C)(C)C)C(C)(C)C)(C)(C)C.CC(C)([O-])C.[Na+]>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>[Br:18][C:19]1[CH:24]=[CH:23][C:22]([N:7]([C:1]2[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=2)[C:8]2[C:17]3[C:12](=[CH:13][CH:14]=[CH:15][CH:16]=3)[CH:11]=[CH:10][CH:9]=2)=[CH:21][CH:20]=1

Participants

7

Reactant 4

HCID 7013Phenyl-1-naphthylamineHCID 115221-Bromo-4-iodobenzeneHCID 83681Tris(1,1-dimethylethyl)phosphineHCID 23676156Sodium t-butoxide

Product 1

HCID 18398525N-(4-Bromophenyl)-N-phenyl-1-naphthylamineYield 62%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolvent

Conditions

Temperature
85 °C

Procedure

Compound 4 [Xu, H.; Yin, K.; Huang, W. Chem. Eur. J. 2007, 13(36), 10281-10293] was prepared as follows: a mixture of N-phenylnaphthalen-1-amine (2.767 g, 12.62 mmol), 1-bromo-4-iodobenzene (7.140 g, 25.24 mmol), tris(dibenzylideneacetone)dipalladium(0) (0.578 g, 0.631 mmol), tri-tert-butylphosphine (10 wt. % in hexanes) (5.83 mL, 1.89 mmol), sodium tert-butoxide (NaOtBu) (3.032 g, 31.55 mmol) and anhydrous toluene (80 mL) was degassed with argon for about 40 min while stirring. The reaction mixture was then maintained under argon at about 85° C. while stirring. Upon confirming consumption of the starting material by TLC (SiO2, 100% hexanes), the reaction was cooled to RT and poured over EtOAc (ca. 300 mL). The organics were then washed with sat. NaHCO3, H2O (2×) and brine, dried over MgSO4, filtered and concentrated in vacuo. Purification of the crude product via flash chromatography (SiO2, 8:1-hexanes:CH2Cl2) provided Compound 4 (2.93 g, 62%) as a white foam: confirmed by LCMS (APCI): calculated for C22H16BrN (M+): 374; Found: 374.

Workup

  1. customCompound 4 [Xu, H.; Yin, K.; Huang, W. Chem. Eur. J. 2007, 13(36), 10281-10293] was prepared
  2. customwas degassed with argon for about 40 min
  3. stirringwhile stirring
  4. customconsumption of the starting material by TLC (SiO2, 100% hexanes)
  5. temperaturethe reaction was cooled to RT
  6. additionpoured over EtOAc (ca. 300 mL)
  7. washThe organics were then washed with sat. NaHCO3, H2O (2×) and brine
  8. dry with materialdried over MgSO4
  9. filtrationfiltered
  10. concentrationconcentrated in vacuo
  11. customPurification of the crude product via flash chromatography (SiO2, 8:1-hexanes:CH2Cl2)

Sources & evidence

ORD record
ord-6694424acd3649fe886cb24fed6b2f9a
Source dataset
uspto-grants-2015_08
Patent number
US09112159B2

Linked notes

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