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

HRID 1786784Notes

Reaction equation

HRID 1786784 reaction equation
[C:1]1([N:7]([C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)[C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.BrC1C=CC([O:27][CH3:28])=CC=1.C[C:30](C)([O-:32])C.[Na+].NC1C=CC=CC=1>C1(C)C=CC=CC=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]>[CH3:30][O:32][C:17]1[CH:16]=[CH:15][C:14]([N:7]([C:1]2[CH:2]=[CH:3][C:4]([O:27][CH3:28])=[CH:5][CH:6]=2)[C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)=[CH:19][CH:18]=1

Participants

8

Reactant 4

HCID 6115AnilineHCID 77304-BromoanisoleHCID 11775TriphenylamineHCID 23676156Sodium t-butoxide

Product 1

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

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolventHCID 57417360Sodium chloride; waterSolvent

Procedure

The synthesis of the triphenylamine donor Wittig salt follows the schematic in FIG. 9. 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(diphenylphosphine)-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 tert-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. Thin layer chromatography was used to monitor the complete formation of the decoupled product. The reaction solution was then worked up with brine washings (3×), 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 give 21.19 g of white solid. 1H NMR (CDCl3): δ3.87 (s, 6H), δ6.87-7.08 (m, 11H), δ7.26 (d, 2H).

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-1040bb9109804361a895bd4cd40aee37
Source dataset
uspto-grants-2009_03
Patent number
US07507840B2

Reaction notes

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