p-Toluidine → 4-Methoxy-4'-methyldiphenylamine

HRID 1282474Notes

Reaction equation

[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([CH3:8])=[CH:4][CH:3]=1.I[C:10]1[CH:15]=[CH:14][C:13]([O:16][CH3:17])=[CH:12][CH:11]=1.CC(C)([O-])C.[Na+].C1(C(C2C=CC=CC=2)=C(P(C2CCCCC2)C2CCCCC2)C)C=CC=CC=1.[Cl-].[NH4+]>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.O1CCOCC1>[CH3:17][O:16][C:13]1[CH:14]=[CH:15][C:10]([NH:1][C:2]2[CH:7]=[CH:6][C:5]([CH3:8])=[CH:4][CH:3]=2)=[CH:11][CH:12]=1

Participants

Conditions

Temperature: 100 °C

Procedure

Into a reactor were introduced 0.214 g (2.00 mmol) of p-toluidine and 4 mL of dioxane under a nitrogen atmosphere. The amine was dissolved in the solvent. To this solution were added 0.515 g (2.2 mol) of p-iodoanisole, 0.231 g (2.4 mmol) of sodium t-butoxide, 4.5 mg (1 mol % based on the amine) of palladium acetate, and 15.6 mg (2 mmol % based on the amine) of the 1,1-diphenyl-2-(dicyclohexylphosphino)propene obtained in Example 2. The resultant reaction mixture was stirred at 100° C. for 8 hours and then cooled. Saturated aqueous ammonium chloride solution was added thereto, and this mixture was extracted with toluene. The extract was dried with anhydrous magnesium sulfate. Thereafter, the solvent was removed under reduced pressure. The concentrate was purified by column chromatography to obtain 0.351 g (82%) of N-p-methoxyphenyl-N-p-tolylamine as yellow crystals. The results obtained are shown in Table 20.

Workup

customThe resultant reaction mixture
temperaturecooled
extractionthis mixture was extracted with toluene
dry with materialThe extract was dried with anhydrous magnesium sulfate
customThereafter, the solvent was removed under reduced pressure
customThe concentrate was purified by column chromatography

Sources & evidence

ORD record: ord-a3c4d2f98fbd407097fc8f701c8ae2b8
Source dataset: uspto-grants-2002_09
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US06455720B1

Reaction notes

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