Methanol → Methyl 4-t-butyl-3-nitrobenzoate

HRID 1418172Notes

Reaction equation

HRID 1418172 reaction equation
[C:1](Cl)(=O)C(Cl)=O.[C:7]([C:11]1[CH:19]=[CH:18][C:14]([C:15]([OH:17])=[O:16])=[CH:13][C:12]=1[N+:20]([O-:22])=[O:21])([CH3:10])([CH3:9])[CH3:8].N1C=CC=CC=1.CO>C(Cl)Cl.CN(C)C=O>[C:7]([C:11]1[CH:19]=[CH:18][C:14]([C:15]([O:17][CH3:1])=[O:16])=[CH:13][C:12]=1[N+:20]([O-:22])=[O:21])([CH3:10])([CH3:8])[CH3:9]

Participants

7

Reactant 4

HCID 887MethanolHCID 1049PyridineHCID 65578Oxalyl chlorideHCID 7388134-Tert-butyl-3-nitrobenzoic acid

Product 1

HCID 19348444Methyl 4-t-butyl-3-nitrobenzoateYield 101.8%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 6344DichloromethaneSolvent

Procedure

13 ml (0.15 mol) of oxalyl chloride were added, with ice-cooling, to a solution of 20.9 g (0.094 mol) of 4-t-butyl-3-nitrobenzoic acid in 200 ml of methylene chloride, and then 0.3 ml of dimethylformamide was added to the resulting mixture. After this addition, the temperature of the reaction mixture was allowed to rise to room temperature, and the mixture was then stirred at room temperature for 4 hours. At the end of this time, any excess of the reagent and the solvent were removed by distillation under reduced pressure, and the residue was again dissolved in 150 ml of methylene chloride. 19 ml (0.25 mol) of pyridine and 6.0 ml (0.15 mol) of methanol were then added, with ice-cooling, to the solution, and the resulting mixture was stirred for 30 minutes with ice-cooling and then at room temperature for 30 minutes. At the end of this time, the reaction was quenched by adding water, the solvent was removed by distillation under reduced pressure, and the residue was extracted with ethyl acetate. The extract was washed with 2N aqueous hydrochloric acid, with water, with a saturated aqueous solution of sodium hydrogencarbonate and with water, in that order, and the solvent was removed by distillation under reduced pressure, to give 22.7 g of the title compound as an oily substance.

Workup

  1. additionAfter this addition
  2. customto rise to room temperature
  3. customAt the end of this time, any excess of the reagent and the solvent were removed by distillation under reduced pressure
  4. dissolutionthe residue was again dissolved in 150 ml of methylene chloride
  5. temperaturecooling, to the solution
  6. stirringthe resulting mixture was stirred for 30 minutes with ice-
  7. temperaturecooling
  8. waitat room temperature for 30 minutes
  9. customAt the end of this time, the reaction was quenched
  10. additionby adding water
  11. customthe solvent was removed by distillation under reduced pressure
  12. extractionthe residue was extracted with ethyl acetate
  13. washThe extract was washed with 2N aqueous hydrochloric acid, with water, with a saturated aqueous solution of sodium hydrogencarbonate and with water, in that order
  14. customthe solvent was removed by distillation under reduced pressure

Sources & evidence

ORD record
ord-d14ebf89e25143c7a8cdda5a03db1079
Source dataset
uspto-grants-1999_03
Patent number
US05880147

Reaction notes

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