Hydrochloric Acid → Diethyl (4-cyano-2-nitrophenyl)malonate

HRID 1386339Notes

Reaction equation

HRID 1386339 reaction equation
[C:1]([O:9][CH2:10][CH3:11])(=[O:8])[CH2:2][C:3]([O:5][CH2:6][CH3:7])=[O:4].[H-].[Na+].Cl[C:15]1[CH:20]=[CH:19][C:18]([C:21]#[N:22])=[CH:17][C:16]=1[N+:23]([O-:25])=[O:24].Cl>CN(C=O)C>[C:21]([C:18]1[CH:19]=[CH:20][C:15]([CH:2]([C:3]([O:5][CH2:6][CH3:7])=[O:4])[C:1]([O:9][CH2:10][CH3:11])=[O:8])=[C:16]([N+:23]([O-:25])=[O:24])[CH:17]=1)#[N:22]

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 7761Diethyl MalonateHCID 13655Benzonitrile, 4-chloro-3-nitro-HCID 24758Sodium hydride

Product 1

HCID 53993532Diethyl (4-cyano-2-nitrophenyl)malonateYield 97.2%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Procedure

Diethyl malonate (44.6ml, 293 mmol) was added dropwise over 1.5 hours to a suspension of sodium hydride (11.7 g of a 60% suspension in mineral oil, 293 mmol) in DMF under argon and the reaction mixture was stirred at ambient temperature for 30 minutes. The resulting solution was added dropwise over 1 hour to a solution of 2-chloro-5-cyano-1-nitrobenzene (24.3 g, 133 mmol) in DMF (75 ml) cooled with a dry ice/acetone bath. The temperature of the cooling bath was adjusted to prevent the freezing of the red reaction mixture. After the addition was completed, the reaction was left to rise to ambient temperature over 2 hours. The resulting red solution was poured slowly into a stirred mixture of ice (100 ml) and 1M hydrochloric acid (10 ml). The resulting yellow precipitate was collected by filtration, washed with water until the filtrate was at pH7.0 and then dried under vacuum to give diethyl (4-cyano-2-nitrophenyl)malonate (39.6 g, 97%).

Workup

  1. temperaturecooled with a dry ice/acetone bath
  2. customthe freezing of the red reaction mixture
  3. additionAfter the addition
  4. waitthe reaction was left
  5. waitto rise to ambient temperature over 2 hours
  6. filtrationThe resulting yellow precipitate was collected by filtration
  7. washwashed with water until the filtrate
  8. customdried under vacuum

Sources & evidence

ORD record
ord-e255ff6bdc544b11aa46a46da636e6f1
Source dataset
uspto-grants-2001_07
Patent number
US06265411B1

Reaction notes

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