Malonic Acid → Benzoic acid, 4-(2-carboxyethenyl)-, methyl ester

HRID 428783Notes

Reaction equation

HRID 428783 reaction equation
[CH:1]([C:3]1[CH:12]=[CH:11][C:6]([C:7]([O:9][CH3:10])=[O:8])=[CH:5][CH:4]=1)=O.C(O)(=O)[CH2:14][C:15]([OH:17])=[O:16].N1C=CC=CC=1.N1CCCCC1>O>[C:7]([C:6]1[CH:11]=[CH:12][C:3]([CH:1]=[CH:14][C:15]([OH:17])=[O:16])=[CH:4][CH:5]=1)([O:9][CH3:10])=[O:8]

Participants

6

Reactant 4

HCID 867Malonic AcidHCID 1049PyridineHCID 8082PiperidineHCID 15294Methyl 4-Formylbenzoate

Product 1

HCID 86881Benzoic acid, 4-(2-carboxyethenyl)-, methyl esterYield 93.9%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
50 °C

Procedure

To a 3-L three-necked round-bottom flask equipped with an overhead stirrer, condenser, and a nitrogen/thermocouple unit was added methyl p-formylbenzoate (82.08 g, 0.50 mole), malonic acid (104.06 g, 1.00 mole), and pyridine (200 mL). Stirring was started followed by heating to 50° C. for 75 minutes. By this time, a sizable amount of solids had formed and to this mixture was added piperidine (7.5 mL, 0.076 mole) and the temperature raised to 80° C. After another one hour at 80° C., the temperature was raised to 115° C. After another 2.5 hours at this temperature, heating was stopped and the mixture allowed to cool before pouring into water (2 L). To the aqueous mixture was carefully added concentrated HCI (250-300 mL) until the mixture became acidic. The mixture was filtered, and the solids washed with fresh water (1 L) before being suction dried. A yield of 96.83 g (93.9 percent) of white solids was obtained. Proton nmr (DMSO-d6) delta: 7.95 (2H, d); 7.80 (2H, d); 7.60 (1H, d); 6.62 (1H, d); 3.82 (3H, s).

Workup

  1. customTo a 3-L three-necked round-bottom flask equipped with an overhead stirrer, condenser
  2. customBy this time, a sizable amount of solids had formed and to this mixture
  3. temperaturethe temperature raised to 80° C
  4. temperaturethe temperature was raised to 115° C
  5. waitAfter another 2.5 hours at this temperature
  6. temperatureheating
  7. temperatureto cool
  8. additionTo the aqueous mixture was carefully added
  9. concentrationconcentrated HCI (250-300 mL) until the mixture
  10. filtrationThe mixture was filtered
  11. washthe solids washed with fresh water (1 L)
  12. customdried

Sources & evidence

ORD record
ord-d0f1a028fee349819d31efafba64da3f
Source dataset
uspto-grants-2001_11
Patent number
US06313340B1

Reaction notes

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