Ethyl Acetate → 4-Bromo-4',4''-dimethoxytriphenylamine

HRID 84993Notes

Reaction equation

HRID 84993 reaction equation
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([N:9]([C:16]2[CH:21]=[CH:20][C:19]([O:22][CH3:23])=[CH:18][CH:17]=2)[C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=2)=[CH:5][CH:4]=1.[Br:24]N1C(=O)CCC1=O.C(OC(=O)C)C>CN(C)C=O>[Br:24][C:13]1[CH:14]=[CH:15][C:10]([N:9]([C:6]2[CH:7]=[CH:8][C:3]([O:2][CH3:1])=[CH:4][CH:5]=2)[C:16]2[CH:17]=[CH:18][C:19]([O:22][CH3:23])=[CH:20][CH:21]=2)=[CH:11][CH:12]=1

Participants

5

Reactant 3

HCID 8857Ethyl AcetateHCID 67184N-bromobutanimideHCID 105430434-Methoxy-N-(4-methoxyphenyl)-N-phenylaniline

Product 1

HCID 105961614-Bromo-4',4''-dimethoxytriphenylamine

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Procedure

2. N,N-bis(4-methoxyphenyl)aniline 1 (9.0 g, 29.5 mmol) was dissolved in 100 mL dimethylformamide in a 250 mL round bottom flask. N-bromosuccinimide (5.25 g, 29.5 mmol) was dissolved in 30 mL dimethylformamide and added dropwise to the reaction mixture. The reaction was allowed to stir at room temperature while being monitored by thin layer chromatography (TLC) (Reaction Time=23 h). The reaction mixture was quenched using 600 mL water and extracted with 4×150 mL dichloromethane. The organic layers were combined and washed with 4×150 mL saturated sodium thiosulfate solution and dried over sodium sulfate. The solvent was removed under reduced pressure. The product was purified along with materials prepared previously using flash chromatography on silica gel eluting with 5:1 hexanes:ethylacetate (12.1 g, 100%). 1H NMR (300 MHz, CDCl3) δ 7.28 (d, J=9.0 Hz, 2H), 7.05 (d, J=9.0 Hz, 4H), 6.90 (d, J=9.0 Hz, 4H), 6.73 (d, J=9.0 Hz, 2H), 3.77 (s, 6H).

Workup

  1. additionadded dropwise to the reaction mixture
  2. customwhile being monitored by thin layer chromatography (TLC) (Reaction Time=23 h)
  3. customThe reaction mixture was quenched
  4. extractionextracted with 4×150 mL dichloromethane
  5. washwashed with 4×150 mL saturated sodium thiosulfate solution
  6. dry with materialdried over sodium sulfate
  7. customThe solvent was removed under reduced pressure
  8. customThe product was purified along with materials
  9. customprepared previously

Sources & evidence

ORD record
ord-844f93307fae4200a82776709e8e9fec
Source dataset
uspto-grants-2014_09
Patent number
US08846978B2

Reaction notes

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