4-Nitrophenol → HCID 13839927, compound

HRID 127974Notes

Reaction equation

HRID 127974 reaction equation
[N+:1]([C:4]1[CH:9]=[CH:8][C:7]([OH:10])=[CH:6][CH:5]=1)([O-:3])=[O:2].C(=O)([O-])[O-].[K+].[K+].Br[C:18]([CH3:25])([CH3:24])[C:19]([O:21][CH2:22][CH3:23])=[O:20]>CC(=O)CC>[CH3:24][C:18]([O:10][C:7]1[CH:8]=[CH:9][C:4]([N+:1]([O-:3])=[O:2])=[CH:5][CH:6]=1)([CH3:25])[C:19]([O:21][CH2:22][CH3:23])=[O:20]

Participants

5

Reactant 3

HCID 9804-NitrophenolHCID 11430Potassium Carbonate2×HCID 11745Propanoic acid, 2-bromo-2-methyl-, ethyl ester2×

Product 1

HCID 13839927HCID 13839927, compoundYield 46%

Reagents, catalysts & solvents 1

HCID 6569Methyl Ethyl KetoneSolvent

Procedure

A mixture of 139.1 g. (1 mol) 4-nitrophenol, 1 liter butan-2-one and 207.3 (1.5 mol) pulverized, anhydrous potassium carbonate is stirred for 2 hours at reflux temperature, then 292.5 g. (1.5 mol) ethyl 2-bromo-2-methylpropionate are added thereto and the reaction mixture maintained at reflux temperature for a further 92 hours. After the addition of a further 69.1 g. (0.5 mol) potassium carbonate and 97.5 g. (0.5 mol) ethyl 2-bromo-2-methyl-propionate, the reaction mixture is stirred for a further 20 hours at reflux temperature. The reaction mixture is then filtered with suction and the filtrate is evaporated in a vacuum (for the removal of excess ethyl ester, finally at a high vacuum). The residue is taken up in diethyl ether, filtered and the ethereal phase now extracted several times with 1 N aqueous sodium hydroxide solution. After washing until neutral and drying, it is evaporated, 153 g. (60% of theory) of an oily crude product being obtained. After distillation at 155.5°-156° C./0.05 mm.Hg., there is obtained a yield of 46% of theory of pure ethyl 2-methyl-2-(4-nitrophenoxy)-propionate in the form of a yellow oil with a refractive index of nD20 =1.5288.

Workup

  1. additionA mixture of 139.1 g
  2. temperatureat reflux temperature
  3. temperaturethe reaction mixture maintained
  4. temperatureat reflux temperature for a further 92 hours
  5. additionAfter the addition of a further 69.1 g
  6. temperatureat reflux temperature
  7. filtrationThe reaction mixture is then filtered with suction
  8. customthe filtrate is evaporated in a vacuum (
  9. customfor the removal of excess ethyl ester
  10. filtrationfiltered
  11. washAfter washing until neutral and
  12. customdrying
  13. customit is evaporated
  14. custom(60% of theory) of an oily crude product being obtained
  15. distillationAfter distillation at 155.5°-156° C./0.05 mm.Hg

Sources & evidence

ORD record
ord-d41dbc5ef3d940dfb7ccd8abb42fcd2d
Source dataset
uspto-grants-1981_03
Patent number
US04258058

Reaction notes

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