Cyanide‐Free One‐Pot Synthesis of Methacrylic Esters from Acetone.

Koyama, Minoru; Kawakami, Takafumi; Okazoe, Takashi; Nozaki, Kyoko

Methacrylic esters, represented by methyl methacrylate (MMA), are widely used as commodity chemicals. Here, the one‐pot synthesis of methacrylic esters from acetone, a haloform and alcohols in the presence of an organic base is described. Using DBU as the organic base for the reaction of acetone, chloroform and methanol in acetonitrile afforded MMA in 66 % yield. When the solvent was replaced by benzonitrile, the product MMA was successfully purified by distillation. Applicability of this process to various alcohols was also investigated to show ethyl, phenyl, CF3CH2, and n‐C6F13CH2CH2 esters were obtained in moderate yields. The use of bromoform instead of chloroform resulted in the improvement of the yield, for example, methyl and n‐C6F13CH2CH2 esters up to 81 and 70 %, respectively. The reaction with deuterated starting materials acetone‐d6 and MeOH‐d4, with DBU in acetonitrile afforded deuterated MMA (MMA‐d8) in 70 % yield.

METHYL methacrylate; ACETONE; ESTERS; ORGANIC bases; METHYL formate

Chemistry - A European Journal, 2019, Vol 25, Issue 46, p10913

0947-6539

Academic Journal

10.1002/chem.201901933