Dimethylformamide → ethyl 2-(4-formyl-2-nitrophenoxy)acetate

HRID 1271199Notes

Reaction equation

HRID 1271199 reaction equation
[OH:1][C:2]1[CH:9]=[CH:8][C:5]([CH:6]=[O:7])=[CH:4][C:3]=1[N+:10]([O-:12])=[O:11].CN(C=O)C.[H-].[Na+].Br[CH2:21][C:22]([O:24][CH2:25][CH3:26])=[O:23]>O1CCCC1>[CH2:25]([O:24][C:22](=[O:23])[CH2:21][O:1][C:2]1[CH:9]=[CH:8][C:5]([CH:6]=[O:7])=[CH:4][C:3]=1[N+:10]([O-:12])=[O:11])[CH3:26]

Participants

6

Reactant 4

HCID 6228DimethylformamideHCID 7748Ethyl bromoacetateHCID 181694-Hydroxy-3-nitrobenzaldehydeHCID 24758Sodium hydride

Product 1

HCID 5305379ethyl 2-(4-formyl-2-nitrophenoxy)acetate

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 4-hydroxy-3-nitrobenzaldehyde (10.0 g, 59.8 mmol) in tetrahydrofuran (600 mL)) and DMF (240 mL) was added dry sodium hydride (1.58 g, 65.82 mmol) and ethyl bromoacetate (7.30 mL, 65.82 mmol). The reaction was refluxed for 24 hours. The reaction was then concentrated and diluted with ethyl acetate (500 mL) and acidified to pH 2 with 1N HCl. The organic layer was then washed with saturated sodium bicarbonate (2×200 mL), sodium chloride (2×200 mL), dried over magnesium sulfate, filtered, and concentrated under reduced pressure to yield a dark red oil. The oil was used in the next step without purification. 1H NMR (d6-DMSO) δ 1.18 (t, 3H), 4.15 (q, 2H), 5.14 (s, 2H), 7.49 (d, 1H), 8.11 (dd, 1H), 8.41 (s, 1H), 9.93 (s, 1H). MS: M+−1=252.1 Da.

Workup

  1. temperatureThe reaction was refluxed for 24 hours
  2. concentrationThe reaction was then concentrated
  3. additiondiluted with ethyl acetate (500 mL)
  4. washThe organic layer was then washed with saturated sodium bicarbonate (2×200 mL), sodium chloride (2×200 mL)
  5. dry with materialdried over magnesium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated under reduced pressure
  8. customto yield a dark red oil
  9. customThe oil was used in the next step without purification

Sources & evidence

ORD record
ord-be3d9676d2334c0286446e73c7a39196
Source dataset
uspto-grants-2007_04
Patent number
US07205295B2

Reaction notes

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