Methyl iodide → N-t-butoxycarbonyl-N-methyl-5-methoxy-2-nitroaniline

HRID 1419106Notes

Reaction equation

HRID 1419106 reaction equation
[C:1]([O:5][C:6]([NH:8][C:9]1[CH:14]=[C:13]([O:15][CH3:16])[CH:12]=[CH:11][C:10]=1[N+:17]([O-:19])=[O:18])=[O:7])([CH3:4])([CH3:3])[CH3:2].[H-].[Na+].[CH3:22]I>CN(C)C=O>[C:1]([O:5][C:6]([N:8]([CH3:22])[C:9]1[CH:14]=[C:13]([O:15][CH3:16])[CH:12]=[CH:11][C:10]=1[N+:17]([O-:19])=[O:18])=[O:7])([CH3:4])([CH3:2])[CH3:3]

Participants

5

Reactant 3

HCID 6328Methyl iodideHCID 24758Sodium hydrideHCID 10199249tert-Butyl (5-methoxy-2-nitrophenyl)carbamate

Product 1

HCID 15544600N-t-butoxycarbonyl-N-methyl-5-methoxy-2-nitroaniline

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Procedure

A solution of 49.6 g of N-t-butoxycarbonyl-5-methoxy-2-nitroaniline (prepared as described in Preparation 6) in 300 ml of dehydrated dimethylformamide was added, whilst ice-cooling, to a suspension of 12.0 g of sodium hydride (as a 55% w/w dispersion in mineral oil) in 300 ml of dehydrated dimethylformamide, and the resulting mixture was stirred at room temperature for 30 minutes, after which 17.2 ml of methyl iodide were added at room temperature. The reaction mixture was stirred for 1 hour, after which it was allowed to stand overnight at room temperature. It was then concentrated to about one-fifth of its original volume by evaporation under reduced pressure. The concentrate was mixed with ice-water and the resulting aqueous mixture was extracted with ethyl acetate. The extract was washed with water and with a saturated aqueous solution of sodium chloride, in that order, after which it was dried over anhydrous sodium sulfate. On distilling off the solvent, there were obtained 52.1 g of the title compound, melting at 122°-124° C.

Workup

  1. stirringThe reaction mixture was stirred for 1 hour
  2. waitto stand overnight at room temperature
  3. concentrationIt was then concentrated to about one-fifth of its original volume by evaporation under reduced pressure
  4. additionThe concentrate was mixed with ice-water
  5. extractionthe resulting aqueous mixture was extracted with ethyl acetate
  6. washThe extract was washed with water and with a saturated aqueous solution of sodium chloride, in that order
  7. dry with materialafter which it was dried over anhydrous sodium sulfate
  8. distillationOn distilling off the solvent

Sources & evidence

ORD record
ord-0c43ec39650a4195ab9d604ecfd57d66
Source dataset
uspto-grants-1999_03
Patent number
US05886014

Reaction notes

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