Hydrochloric Acid → HCID 70559053, compound

HRID 2173401Notes

Reaction equation

HRID 2173401 reaction equation
[CH3:1][O:2][C:3]1[CH:8]=[C:7](Cl)[CH:6]=[CH:5][C:4]=1[N+:10]([O-:12])=[O:11].[H-].[Na+].[CH2:15]([C:21]([O:23][CH2:24][CH3:25])=[O:22])[C:16]([O:18][CH2:19][CH3:20])=[O:17].Cl>CN(C=O)C>[CH3:1][O:2][C:3]1[CH:8]=[C:7]([CH:15]([C:16]([O:18][CH2:19][CH3:20])=[O:17])[C:21]([O:23][CH2:24][CH3:25])=[O:22])[CH:6]=[CH:5][C:4]=1[N+:10]([O-:12])=[O:11]

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 7761Diethyl MalonateHCID 24758Sodium hydrideHCID 811105-Chloro-2-nitroanisole

Product 1

HCID 70559053HCID 70559053, compound

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

A solution of 5-chloro-2-nitrophenyl methyl ether (5 g, 26.596 mmol) in dry DMF (150 mL) was cooled to 0° C. by ice water and NaH (3.51 g, 87.750 mmol, 60% purity) was added portionwise, and then the reaction was warmed to ambient temperature and stirred for 1.5 hours. The reaction was cooled to 0° C. and CH2(COOEt)2 (14.04 g, 87.768 mmol) was added. The result mixture was warmed to ambient temperature and heated to 80° C. for 13 hours. The reaction was cooled to ambient temperature and poured into ice water and added 2N HCl to adjust pH to 3. Extracted with EtOAc and the organic layer was washed with water, brine, dried over anhydrous sodium sulfate and concentrated. The crude product was purified via column chromatograph to afford diethyl (3-methoxy-4-nitrophenyl)propanedioate. 1H-NMR (400 MHz, CDCl3) δ ppm 7.86 (d, J=8.3 Hz, 1H), 7.25 (s, 1H), 7.07 (d, J=8.3 Hz, 1H), 4.67 (s, 1H), 4.23˜4.29 (m, 4H), 4.00 (s, 3H), 1.31 (t, J=7.0 Hz, 6H).

Workup

  1. additionwas added portionwise
  2. temperatureThe reaction was cooled to 0° C.
  3. temperatureThe result mixture was warmed to ambient temperature
  4. temperatureheated to 80° C. for 13 hours
  5. temperatureThe reaction was cooled to ambient temperature
  6. extractionExtracted with EtOAc
  7. washthe organic layer was washed with water, brine
  8. dry with materialdried over anhydrous sodium sulfate
  9. concentrationconcentrated
  10. customThe crude product was purified via column chromatograph

Sources & evidence

ORD record
ord-071616409a89467bb567823f3a0fa806
Source dataset
uspto-grants-2015_06
Patent number
US09056859B2

Reaction notes

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