3-Nitrophenol → Diethyl 2-methyl-2-(3-nitrophenoxy)malonate

HRID 2277851Notes

Reaction equation

HRID 2277851 reaction equation
Br[C:2]([CH3:13])([C:8]([O:10][CH2:11][CH3:12])=[O:9])[C:3]([O:5][CH2:6][CH3:7])=[O:4].[F-].[K+].[N+:16]([C:19]1[CH:20]=[C:21]([OH:25])[CH:22]=[CH:23][CH:24]=1)([O-:18])=[O:17]>CN(C=O)C.O>[CH3:13][C:2]([O:25][C:21]1[CH:22]=[CH:23][CH:24]=[C:19]([N+:16]([O-:18])=[O:17])[CH:20]=1)([C:8]([O:10][CH2:11][CH3:12])=[O:9])[C:3]([O:5][CH2:6][CH3:7])=[O:4]

Participants

6

Reactant 3

HCID 111373-NitrophenolHCID 94944Diethyl bromomethylmalonateHCID 522689Potassium Fluoride

Product 1

HCID 22060402Diethyl 2-methyl-2-(3-nitrophenoxy)malonateYield 80%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent

Conditions

Temperature
60 °C

Procedure

Diethyl 2-bromo-2-methylmalonate (1.0 g, 3.95 mmole) was added to a stirred suspension of potassium fluoride (0.57 g, 9.8 mmole) in dry DMF (5 mL). After stifling for 20 min at room temperature, 3-nitrophenol (0.55 g, 3.95 mmole) was added. The resulting mixture was stirred at 60° C. for 6 h, cooled to room temperature, diluted with water (30 mL) and extracted with ethyl acetate (3×200 mL). The organic layer was washed with aq. 1N NaOH (2×75 mL), dried over anhydrous Na2SO4, filtered and evaporated in vacuo to provide diethyl 2-methyl-2-(3-nitrophenoxy)malonate (0.89 g, 80%). 1H NMR (CDCl3): δ 7.92 (dd, 1H, J=2.3 and 8.2 Hz), 7.82 (t, 1H, J=2.3 Hz), 7.41 (t, 1H, J=8.2 Hz), 7.30 (dd, 1H, J=2.3 and 8.2 Hz), 4.28 (qt, 4H, J=7.0 Hz), 1.81 (s, 3H), 1.26 (t, 6H, J=7.0 Hz).

Workup

  1. temperaturecooled to room temperature
  2. extractionextracted with ethyl acetate (3×200 mL)
  3. washThe organic layer was washed with aq. 1N NaOH (2×75 mL)
  4. dry with materialdried over anhydrous Na2SO4
  5. filtrationfiltered
  6. customevaporated in vacuo

Sources & evidence

ORD record
ord-942c789c9e5d4a0c8e5e054b08df8201
Source dataset
uspto-grants-2015_09
Patent number
US09133133B2

Reaction notes

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