Cesium carbonate → N-[3-(4-amino-2-nitrophenoxy)phenyl]-3-(1-cyano-1-methylethyl)benzamide

HRID 1097501Notes

Reaction equation

HRID 1097501 reaction equation
[C:1]([C:3]([C:6]1[CH:7]=[C:8]([CH:19]=[CH:20][CH:21]=1)[C:9]([NH:11][C:12]1[CH:17]=[CH:16][CH:15]=[C:14]([OH:18])[CH:13]=1)=[O:10])([CH3:5])[CH3:4])#[N:2].F[C:23]1[CH:29]=[CH:28][C:26]([NH2:27])=[CH:25][C:24]=1[N+:30]([O-:32])=[O:31].C(=O)([O-])[O-].[Cs+].[Cs+]>CN(C)C=O>[NH2:27][C:26]1[CH:28]=[CH:29][C:23]([O:18][C:14]2[CH:13]=[C:12]([NH:11][C:9](=[O:10])[C:8]3[CH:19]=[CH:20][CH:21]=[C:6]([C:3]([C:1]#[N:2])([CH3:5])[CH3:4])[CH:7]=3)[CH:17]=[CH:16][CH:15]=2)=[C:24]([N+:30]([O-:32])=[O:31])[CH:25]=1

Participants

5

Reactant 3

HCID 10796Cesium carbonateHCID 677684-Fluoro-3-nitroanilineHCID 573868253-(1-cyano-1-methylethyl)-N-(3-hydroxyphenyl)benzamide

Product 1

HCID 66810369N-[3-(4-amino-2-nitrophenoxy)phenyl]-3-(1-cyano-1-methylethyl)benzamideYield 82%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
80 °C

Procedure

To a solution of 3-(1-cyano-1-methylethyl)-N-(3-hydroxyphenyl)benzamide (20 g, 71.3 mmol) produced in Example 1(i) and 4-fluoro-3-nitroaniline (10.9 g, 69.9 mmol) in N,N-dimethylformamide (150 mL) was added cesium carbonate (33.8 g, 104 mmol), and the mixture was stirred at 80° C. for 16 hr. The reaction mixture was cooled to room temperature, insoluble material was filtered off and washed with ethyl acetate. The filtrate and washings were combined and the mixture was concentrated under reduced pressure. The obtained residue was diluted with ethyl acetate (300 mL), washed successively with water (300 ml) and saturated brine (150 mL×2), and dried over anhydrous sodium sulfate. Insoluble material was filtered off, and the filtrate was concentrated under reduced pressure. The obtained residue was purified by basic silica gel column chromatography (eluate: ethyl acetate), and the obtained solution was concentrated under reduced pressure. The residue was crystallized from ethyl acetate/n-hexane to give the title compound (23.8 g, 82%) as a red-orange powder.

Workup

  1. temperatureThe reaction mixture was cooled to room temperature
  2. filtrationinsoluble material was filtered off
  3. washwashed with ethyl acetate
  4. concentrationthe mixture was concentrated under reduced pressure
  5. additionThe obtained residue was diluted with ethyl acetate (300 mL)
  6. washwashed successively with water (300 ml) and saturated brine (150 mL×2)
  7. dry with materialdried over anhydrous sodium sulfate
  8. filtrationInsoluble material was filtered off
  9. concentrationthe filtrate was concentrated under reduced pressure
  10. customThe obtained residue was purified by basic silica gel column chromatography (eluate: ethyl acetate)
  11. concentrationthe obtained solution was concentrated under reduced pressure
  12. customThe residue was crystallized from ethyl acetate/n-hexane

Sources & evidence

ORD record
ord-91cc9b0e901e4ea7b26cfdce0affbed7
Source dataset
uspto-grants-2012_03
Patent number
US08143258B2

Reaction notes

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