Diethyl methylmalonate → Propanedioic acid, 2-(3-chloro-4-nitrophenyl)-2-methyl-, 1,3-diethyl ester

HRID 444540Notes

Reaction equation

HRID 444540 reaction equation
[H-].[Na+].[CH3:3][CH:4]([C:10]([O:12][CH2:13][CH3:14])=[O:11])[C:5]([O:7][CH2:8][CH3:9])=[O:6].[Cl:15][C:16]1[CH:21]=[C:20](Cl)[CH:19]=[CH:18][C:17]=1[N+:23]([O-:25])=[O:24]>CN(C)P(N(C)C)(N(C)C)=O.O>[CH3:3][C:4]([C:20]1[CH:19]=[CH:18][C:17]([N+:23]([O-:25])=[O:24])=[C:16]([Cl:15])[CH:21]=1)([C:5]([O:7][CH2:8][CH3:9])=[O:6])[C:10]([O:12][CH2:13][CH3:14])=[O:11]

Participants

6

Reactant 3

HCID 11857Diethyl methylmalonateHCID 118992,4-DichloronitrobenzeneHCID 24758Sodium hydride

Product 1

HCID 12854241Propanedioic acid, 2-(3-chloro-4-nitrophenyl)-2-methyl-, 1,3-diethyl ester

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 12679HexamethylphosphoramideSolvent2×

Procedure

The starting material can also be prepared as follows: 4.8 g 50% sodium hydride in mineral oil are added to 100 ml hexamethylphosphoramide while stirring under nitrogen. Hereupon 17.1 g diethyl α-methylmalonate are added and the mixture slowly heated to 100°. The solution of 19.2 g 2,4-dichloro-nitrobenzene in 20 ml hexamethylphosphoramide is added dropwise during 1/2 hour and the temperature kept at 100° for seven hours. After cooling, the mixture is diluted with water, concentrated in vacuo, the residue taken up in water and extracted with benzene. The extract is washed with water, dried, filtered, evaporated, the residue distilled and the fraction boiling at 147°-148°/0.25 mm Hg collected, to yield the diethyl α-methyl-α-(3-chloro-4-nitrophenyl)-malonate. (The analogously prepared diethyl α-ethyl-α-(3-chloro-4-nitrophenyl)-malonate boils at 170°-174°/1 mm Hg.)

Workup

  1. customThe starting material can also be prepared
  2. temperaturethe mixture slowly heated to 100°
  3. temperatureAfter cooling
  4. concentrationconcentrated in vacuo
  5. extractionextracted with benzene
  6. washThe extract is washed with water
  7. customdried
  8. filtrationfiltered
  9. customevaporated
  10. distillationthe residue distilled
  11. customthe fraction boiling at 147°-148°/0.25 mm Hg collected

Sources & evidence

ORD record
ord-d8683b5bfd45400ca7eccff93653459e
Source dataset
uspto-grants-1981_04
Patent number
US04264619

Reaction notes

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