p-Toluidine → N-Phenyl-p-toluidine

HRID 1596840Notes

Reaction equation

HRID 1596840 reaction equation
[C:1]1(Cl)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[NH2:8][C:9]1[CH:14]=[CH:13][C:12]([CH3:15])=[CH:11][CH:10]=1.CC([O-])(C)C.[Na+]>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:1]1([NH:8][C:9]2[CH:14]=[CH:13][C:12]([CH3:15])=[CH:11][CH:10]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1

Participants

6

Reactant 3

HCID 7813p-ToluidineHCID 7964ChlorobenzeneHCID 23676156Sodium t-butoxide

Product 1

HCID 12109N-Phenyl-p-toluidineYield 44%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolvent

Procedure

The general procedure from Example 1 was followed using PhCl (122 μl, 1.2 mmol) and p-toluidine (108 mg, 1.0 mmol) with Pd2(dba)3 (20 mg, 0.0218 mmol) and (Me3C)2PH(O) (14.5 mg, 0.0878 mmol) and NaOtBu (144 mg, 1.5 mmol) in 3.0 mL of toluene. After 12 h, the reaction mixture was chromatographed with 5% ethyl acetate/hexane to give 80 mg (44% yield) of N-phenyl-p-toluidine. It was >95% pure by 1H NMR and GC/MS. 1H NMR (500 MHz, CDCl3): δ 7.13 (t, J=7.91 Hz, 2H), 6.98 (m, 2H), 6.89 (m, 4H), 6.78 (t, J=7.32 Hz, 1H), 5.46 (s, br. 1H), 2.20 (s, 3H) ppm. 13C NMR (125 MHz, CDCl3): d 143.9, 140.3, 130.8, 129.8, 129.2, 120.2, 118.9, 116.8, 20.6 ppm. MS: Calculated for C13H13N(M+): 183.3. Found: 184.1 (M++H).

Workup

  1. customthe reaction mixture was chromatographed with 5% ethyl acetate/hexane

Sources & evidence

ORD record
ord-9715d1074ec44029803f0dd2b76a64dd
Source dataset
uspto-grants-2001_09
Patent number
US06291722B1

Reaction notes

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