Sodium hydride → HCID 11603852, compound

HRID 751355Notes

Reaction equation

HRID 751355 reaction equation
[C:1]([O:14][CH2:15][C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1)(=[O:13])[CH2:2][C:3]([O:5][CH2:6][C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1)=[O:4].[H-].[Na+].Cl[C:25]1[CH:30]=[CH:29][N:28]=[CH:27][C:26]=1[N+:31]([O-:33])=[O:32]>C1(C)C=CC=CC=1>[CH2:6]([O:5][C:3](=[O:4])[CH:2]([C:25]1[CH:30]=[CH:29][N:28]=[CH:27][C:26]=1[N+:31]([O-:33])=[O:32])[C:1]([O:14][CH2:15][C:16]1[CH:17]=[CH:18][CH:19]=[CH:20][CH:21]=1)=[O:13])[C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 84754Dibenzyl malonateHCID 27357814-Chloro-3-nitropyridine

Product 1

HCID 11603852HCID 11603852, compoundYield 33.6%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent2×

Procedure

The title compound is prepared following the procedures of Daisley, R. W.; Hanbali, J. R. Synth. Commun., 763, (1981) as follows. Dibenzyl malonate (3.47 mL, 13.9 mmol) is added dropwise to a stirred mixture of 60% oil dispersion of sodium hydride (556 g, 13.9 mmol) in toluene (20 mL). After 1 hr, the mixture is treated with a solution of 4-chloro-3-nitropyridine (2.0 g, 12.6 mmol) in toluene (10 mL) and then heated at reflux for 2 hr. After cooling to room temperature, the reaction is concentrated and the residue is treated with 1M aq hydrochloric acid (6 mL) and extracted with ethyl acetate. The combined extract is washed with saline, dried, filtered and concentrated. The residue is purified by chromatography eluting with pentane-20% ethyl acetate. Product containing fractions are combined and concentrated to give 2-(3-nitropyridin-4-yl)malonic acid dibenzyl ester (1.72 g, 33.6% yield) as a yellow oil.

Workup

  1. customThe title compound is prepared
  2. temperatureheated
  3. temperatureat reflux for 2 hr
  4. concentrationthe reaction is concentrated
  5. additionthe residue is treated with 1M aq hydrochloric acid (6 mL)
  6. extractionextracted with ethyl acetate
  7. extractionThe combined extract
  8. washis washed with saline
  9. customdried
  10. filtrationfiltered
  11. concentrationconcentrated
  12. customThe residue is purified by chromatography
  13. washeluting with pentane-20% ethyl acetate
  14. additionProduct containing fractions
  15. concentrationconcentrated

Sources & evidence

ORD record
ord-0a8a24e1ec4d4cedbff442e99ba14609
Source dataset
uspto-grants-2008_07
Patent number
US07405300B2

Reaction notes

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