Hydrochloric Acid → Dimethyl 2-(4-chloro-2-nitrophenyl)malonate

HRID 1827449Notes

Reaction equation

HRID 1827449 reaction equation
[H-].[Na+].[C:3]([O:10][CH3:11])(=[O:9])[CH2:4][C:5]([O:7][CH3:8])=[O:6].Cl[C:13]1[CH:18]=[C:17](Cl)[CH:16]=[CH:15][C:14]=1[N+:20]([O-:22])=[O:21].[ClH:23].[OH-].[Na+]>CN1C(=O)CCC1>[CH3:8][O:7][C:5](=[O:6])[CH:4]([C:13]1[CH:18]=[CH:17][C:16]([Cl:23])=[CH:15][C:14]=1[N+:20]([O-:22])=[O:21])[C:3]([O:10][CH3:11])=[O:9]

Participants

7

Reactant 5

HCID 313Hydrochloric AcidHCID 7943Dimethyl malonateHCID 118992,4-DichloronitrobenzeneHCID 14798Sodium HydroxideHCID 24758Sodium hydride

Product 1

HCID 2727544Dimethyl 2-(4-chloro-2-nitrophenyl)malonate

Reagents, catalysts & solvents 1

HCID 13387N-methyl-2-pyrrolidoneSolvent

Procedure

To a stirred slurry of NaH (36.0 g, 1500 mmol) in NMP (1.0 L) was added dimethyl malonate (137.4 mL, 1200 mmol) drop wise. The reaction was cooled as needed to keep the internal temperature below 30 degrees Celsius. After gas evolution ceased, 2,4-dichloronitrobenzene (192 g, 1000 mmol) was added to the reaction. It was carefully heated to 65 degrees Celsius until the reaction was complete as determined by HPLC. The reaction was cooled to room temperature, and then poured over 500 mL ice mixed with 150 mL conc. HCl. The pH of the aqueous layer was adjusted to neutral using 1 N NaOH. The solids were removed by filtering through a coarse fritted filter, and rinsed with water (3 L). The yellow solids were allowed to dry overnight. Yield 261.5 g, 91%.

Workup

  1. temperatureThe reaction was cooled
  2. customthe internal temperature below 30 degrees Celsius
  3. temperatureIt was carefully heated to 65 degrees Celsius until the reaction
  4. customThe solids were removed
  5. filtrationby filtering through a coarse fritted filter
  6. washrinsed with water (3 L)
  7. customto dry overnight

Sources & evidence

ORD record
ord-fd156a5d31cb455ba4f0f9d919166103
Source dataset
uspto-grants-2006_05
Patent number
US07053107B2

Reaction notes

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