Reaction #8402

Reaction equation

HCl

benzylmalonic acid

paraformaldehyde

diethylamine

→

2-methylene-3-phenylpropanoic acid

Yield 90.0%

Solvents

water

ethyl acetate

Conditions

Workup

1. 1
   Otherthe reaction temperature below 20° C
2. 2
   TemperatureThe reaction was then warmed
3. 3
   Temperatureto reflux for 90 minutes
4. 4
   Temperaturecooled again on ice
5. 5
   Otherthe reaction temperature below 10° C
6. 6
   OtherThe phases were then separated
7. 7
   WashThe organic layer was washed with brine (100 mL)
8. 8
   Dryingdried over sodium sulfate
9. 9
   Filtrationfiltered
10. 10
    Concentrationthe filtrate concentrated under vacuum

Procedure

A solution of benzylmalonic acid (20.0 g, 0.103 mol, 1 eq) and paraformaldehyde (4.94 g, 0.164 mol, 1.6 eq) in ethyl acetate (150 mL) was cooled (0° C.) and treated with diethylamine (10.65 mL, 0.103 mol, 1 eq) drop wise, keeping the reaction temperature below 20° C. The reaction was then warmed to reflux for 90 minutes and cooled again on ice. The homogeneous solution was treated with water (20 mL) and concentrated aqueous HCl (12N) (9.0 mL, 0.108 mol) drop wise, keeping the reaction temperature below 10° C. The phases were then separated. The organic layer was washed with brine (100 mL), dried over sodium sulfate, filtered, and the filtrate concentrated under vacuum giving 2-methylene-3-phenylpropanoic acid (10) as a white solid (15 g, 90%).

Source