4-Methyl-2-nitrophenol → Ethyl 2-methyl-2-(4-methyl-2-nitrophenoxy)propanoate

HRID 344734Notes

Reaction equation

HRID 344734 reaction equation
[N+:1]([C:4]1[CH:9]=[C:8]([CH3:10])[CH:7]=[CH:6][C:5]=1[OH:11])([O-:3])=[O:2].[H-].[Na+].Br[C:15]([CH3:22])([CH3:21])[C:16]([O:18][CH2:19][CH3:20])=[O:17].[OH-].[Na+]>CN1CCCN(C)C1=O.C(OCC)(=O)C>[CH3:21][C:15]([O:11][C:5]1[CH:6]=[CH:7][C:8]([CH3:10])=[CH:9][C:4]=1[N+:1]([O-:3])=[O:2])([CH3:22])[C:16]([O:18][CH2:19][CH3:20])=[O:17]

Participants

7

Reactant 4

HCID 83914-Methyl-2-nitrophenolHCID 11745Propanoic acid, 2-bromo-2-methyl-, ethyl esterHCID 14798Sodium HydroxideHCID 24758Sodium hydride

Product 1

HCID 4507462Ethyl 2-methyl-2-(4-methyl-2-nitrophenoxy)propanoateYield 24.9%

Reagents, catalysts & solvents 2

HCID 8857Ethyl AcetateSolventHCID 816462(1H)-Pyrimidinone, tetrahydro-1,3-dimethyl-Solvent

Procedure

A solution of 2-nitro-4-methylphenol (11.48 g) in 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone (DMPU) (50 ml) was cooled at 5° C. and treated with portions of sodium hydride (55% w/w dispersion in mineral oil, 3.27 g). The mixture was stirred at room temperature for 2 hours, then cooled to 5° C. and treated with ethyl 2-bromo-2-methylpropionate (13.15 g). The mixture was heated at about 100° C. for 18 hours, then cooled to room temperature and poured into a mixture of aqueous sodium hydroxide solution (1M) and ethyl acetate. The organic solution was separated and washed twice with 1M sodium hydroxide solution, then dried (MgSO4) and concentrated. The resulting oil was purified by flash column chromatography, eluting with a mixture of ethyl acetate and hexane, (increasing from 5:95 v/v to 10:90 v/v), to give ethyl 2-methyl-2-(2-nitro-4-methylphenoxy)propionate (4.48 g) as an oil; NMR: 1.25 (3H, t), 1.60(6H, s), 2.35(3H, s), 4.25(2H, q) and 6.8-7.6(3H, m).

Workup

  1. temperaturecooled to 5° C.
  2. temperatureThe mixture was heated at about 100° C. for 18 hours
  3. temperaturecooled to room temperature
  4. customThe organic solution was separated
  5. washwashed twice with 1M sodium hydroxide solution
  6. dry with materialdried (MgSO4)
  7. concentrationconcentrated
  8. customThe resulting oil was purified by flash column chromatography
  9. washeluting with a mixture of ethyl acetate and hexane, (increasing from 5:95 v/v to 10:90 v/v),

Sources & evidence

ORD record
ord-45dd9e86968a45b98eddc8fc4b0e86f0
Source dataset
uspto-grants-1991_10
Patent number
US05053415

Reaction notes

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