Ethyl α-(bromomethyl)acrylate (CAS NO.: ), which is also known as 2-Propenoic acid, 2-(bromomethyl)-,ethyl ester, could be produced through the following synthetic routes.

A. α-(Bromomethyl)acrylic acid (CAS NO.:). A 500-mL, three-necked, round-bottomed flask is equipped with a magnetic stirrer, fraction collector, cold-finger condenser, and two thermometers. Into the flask are placed 55.0 g (0.25 mol) of diethyl bis(hydroxymethyl)malonate and 142 mL (1.25 mol) of 47–49% hydrobromic acid. The mixture is then heated and the temperature of the liquid maintained between 85 and 90°C. A mixture of ethyl bromide and water distills during the course of 1.5–2 hr. The residue is then boiled for 10 hr, maintaining the temperature between 85–90°C. At the end of this period, the mixture is concentrated on a rotary evaporator at 65–70°C (10–15 mm). About 100 mL of water is removed. The residue is cooled in the refrigerator overnight. Crystals of α-(bromomethyl)acrylic acid are filtered in the cold to give, after drying, 17.9 g (43%) of acid, mp 71–73°C.

B. Ethyl α-(bromomethyl)acrylate (CAS NO.: ). In a nitrogen-flushed, 1-L, round-bottomed flask equipped with a magnetic stirrer, Dean-Stark trap, and condenser are placed 42.0 g (0.25 mol) of α-(bromomethyl)acrylic acid and 300 mL of benzene. Approximately 50 mL of a binary azeotrope of benzene and water is distilled. The Dean-Stark trap is removed and 100 mL of absolute ethanol and 1 mL of concentrated sulfuric acid are added slowly. The contents of the flask are boiled in a nitrogen atmosphere for 36 hr, the condensate being passed through 100 g of molecular sieves (Linde 3A) before being returned to the flask. About 125 mL of a mixture of benzene and ethanol is removed from the reaction mixture by distillation (at 67°C). Then 100 mL of benzene is added and another 125 mL of benzene-ethanol mixture distilled (67–75°C). The residue is poured into 200 mL of water and neutralized with solid sodium bicarbonate (ca. 10–15 g) until CO₂ evolution ceases. The resulting solution is extracted with three 75-mL portions of ether, and the combined extracts are dried over anhydrous sodium sulfate for 3 hr. The ether is removed under reduced pressure in a rotary evaporator, and crude ester distilled to give a fraction at 39–40°C (0.9 mm) that weighs 33–34 g (71%). The ester is of high purity, as evidenced by spectral analysis.

Notice: Ethyl α-(bromomethyl) acrylate is a potent vesicant and lachrymator and should be handled with care. All operations should be carried out in an efficiently ventilated hood in order to avoid contact.