Hydrochloric Acid → HCID 10038811, compound

HRID 1392246Notes

Reaction equation

HRID 1392246 reaction equation
C[O-].[Na+].[C:4]([O:11][CH3:12])(=[O:10])[CH2:5][C:6]([O:8][CH3:9])=[O:7].F[C:14]1[CH:19]=[C:18]([F:20])[CH:17]=[CH:16][C:15]=1[N+:21]([O-:23])=[O:22].Cl>C1(C)C=CC=CC=1.CS(C)=O>[F:20][C:18]1[CH:17]=[CH:16][C:15]([N+:21]([O-:23])=[O:22])=[C:14]([CH:5]([C:4]([O:11][CH3:12])=[O:10])[C:6]([O:8][CH3:9])=[O:7])[CH:19]=1

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 7943Dimethyl malonateHCID 679672,4-DifluoronitrobenzeneHCID 10942334Sodium Methoxide

Product 1

HCID 10038811HCID 10038811, compoundYield 76%

Reagents, catalysts & solvents 2

HCID 679Dimethyl SulfoxideSolventHCID 1140TolueneSolvent

Conditions

Temperature
115 °C

Procedure

In a flask made of glass equipped with a stirrer, a thermometer, a distillation device and a dropping funnel and having an inner volume of 500 ml were charged 11.0 g (0.2 mol) of sodium methoxide and 30 ml of dimethyl sulfoxide under argon atmosphere, and the temperature of the mixture was raised to 110 to 120° C. while stirring, then, 27.0 g (0.2 mol) of dimethyl malonate with a purity of 98% was gradually added dropwise to the mixture over 30 minutes, and the resulting mixture was stirred for 2 hours while removing methanol under reduced pressure of 0.010 to 0.013 MPa. Subsequently, the mixture was cooled to 100° C. under the same pressure, 16.2 g (0.1 mol) of 2,4-difluoronitrobenzene with a purity of 98% was gradually added dropwise to the mixture over 30 minutes, and the mixture was further reacted at the same pressure and the same temperature for one hour. After completion of the reaction, the mixture was cooled to room temperature, 100 ml of toluene was added to the mixture and 40 ml (0.2 mol) of 5 mol/l hydrochloric acid was gradually added dropwise to the mixture while stirring. Then, the organic layer was separated, and washed successively with 50 ml of water and 50 ml of a saturated saline solution in this order, and dried over anhydrous magnesium sulfate. This organic layer was analyzed (absolute quantitative method) by high performance liquid chromatography, it can be found that 20.6 g (yield: 76%) of dimethyl 2-(5-fluoro-2-nitrophenyl)malonate was formed.

Workup

  1. customIn a flask made of glass
  2. customequipped with a stirrer
  3. stirringthe resulting mixture was stirred for 2 hours
  4. customwhile removing methanol under reduced pressure of 0.010 to 0.013 MPa
  5. additionwas gradually added dropwise to the mixture over 30 minutes
  6. customthe mixture was further reacted at the same pressure
  7. customAfter completion of the reaction
  8. temperaturethe mixture was cooled to room temperature
  9. additionwas gradually added dropwise to the mixture
  10. stirringwhile stirring
  11. customThen, the organic layer was separated
  12. washwashed successively with 50 ml of water and 50 ml of a saturated saline solution in this order
  13. dry with materialdried over anhydrous magnesium sulfate

Sources & evidence

ORD record
ord-f8431931640f44ddae06006e69a9440b
Source dataset
uspto-grants-2008_03
Patent number
US07342040B2

Reaction notes

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