Toluene → 4-Methoxy-N-(4-methoxyphenyl)-N-phenylaniline

HRID 1786787Notes

Reaction equation

HRID 1786787 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([O:8][CH3:9])=[CH:4][CH:3]=1.C[C:11](C)([O-:13])C.[Na+].[NH2:16][C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1.[C:23]1(C)[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1>[Cl-].[Na+].O.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(P(C2C=CC=CC=2)[C-]2C=CC=C2)C=CC=CC=1.[C-]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C1.[Fe+2]>[CH3:9][O:8][C:5]1[CH:6]=[CH:7][C:2]([N:16]([C:26]2[CH:27]=[CH:28][C:23]([O:13][CH3:11])=[CH:24][CH:25]=2)[C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)=[CH:3][CH:4]=1

Participants

8

Reactant 4

HCID 1140TolueneHCID 6115AnilineHCID 77304-BromoanisoleHCID 23676156Sodium t-butoxide

Product 1

HCID 105430434-Methoxy-N-(4-methoxyphenyl)-N-phenylaniline

Reagents, catalysts & solvents 3

HCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)CatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 57417360Sodium chloride; waterSolvent

Procedure

In a procedure modified from Thayumanavan et al. (Chem Mater., 1997, 9, 3231-3235), to a solution of 4.975 g (5.43 mmol) of tris(dibenzylideneacetone)-dipalladium (0) and 4.519 g (8.15 mmol) of 1,1′-bis(diphenylphosphino)-ferrocene in 680 mL toluene under nitrogen was added 68.46 mL (0.245 mol) of 4-bromoanisole and was allowed to stir for 25 minutes. Then, sodium t-butoxide (59.36 g, 0.618 mol) and aniline (22.5 mL, 0.236 mol) were added to the solution and stirred at 90° C. for approximately 2 weeks. The complete formation of decoupled product was monitored by thin layer chromatography. The reaction solution was then worked up with several (3×) brine washings, extracted with ether, and dried over MgSO4. A flash column of 5% ethyl acetate/95% hexanes gave a light brown solid. The still crude product was purified on a column with 1% ethyl acetate/99% hexanes mobile phase to afford 20.39 g of white solid. 1H NMR (CDCl3): δ3.98 (s, 6H), δ7.01-7.23 (m, 11H), δ7.36 (d, 2H); m/z 305.1 (M+), 290.1 (M+-CH3).

Workup

  1. stirringstirred at 90° C. for approximately 2 weeks
  2. extractionextracted with ether
  3. dry with materialdried over MgSO4
  4. customA flash column of 5% ethyl acetate/95% hexanes gave a light brown solid
  5. customThe still crude product was purified on a column with 1% ethyl acetate/99% hexanes mobile phase

Sources & evidence

ORD record
ord-cadf07805ecd4e3788c8b00b71e01471
Source dataset
uspto-grants-2009_03
Patent number
US07507840B2

Reaction notes

Loading…