Synthesis Reference(s)
Organic Syntheses, Coll. Vol. 7, p. 319, 1990
Synthetic Communications, 16, p. 387, 1986
DOI: 10.1080/00397918608057713
Synthesis
The general procedure for the synthesis of methyl 2-(bromomethyl)acrylate from methyl 2-(hydroxymethyl)acrylate was as follows: 10.2 g of 2-hydroxymethyl methacrylate produced in the previous step was dissolved in 150 mL of acetonitrile, followed by the slow dropwise addition of 4 mL of phosphorus tribromide. After the dropwise addition, the reaction was stirred continuously for 4 hours at room temperature. Upon completion of the reaction, the reaction was quenched by the addition of an appropriate amount of water, followed by removal of the acetonitrile solvent by decompression distillation with a rotary evaporator. To the residue, 100 mL of water was added and extracted twice using ethyl acetate (100 mL each time). The organic phases were combined, dried over anhydrous sodium sulfate and concentrated under reduced pressure to remove the solvent, resulting in 13.5 g of colorless liquid product in 86% yield.
References
[1] Tetrahedron Asymmetry, 2013, vol. 24, # 7, p. 395 - 401
[2] Patent: CN107915668, 2018, A. Location in patent: Paragraph 0018
[3] Organic Letters, 2011, vol. 13, # 15, p. 3864 - 3867
[4] Tetrahedron Letters, 2014, vol. 55, # 13, p. 2075 - 2077
[5] Chemical Communications, 2014, vol. 50, # 96, p. 15216 - 15219
