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Cyanide‐Free One‐Pot Synthesis of Methacrylic Esters from Acetone
Author(s) -
Koyama Minoru,
Kawakami Takafumi,
Okazoe Takashi,
Nozaki Kyoko
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201901933
Subject(s) - chemistry , acetone , acetonitrile , chloroform , yield (engineering) , benzonitrile , solvent , methyl methacrylate , methanol , organic chemistry , polymerization , materials science , metallurgy , polymer
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, CF 3 CH 2 , and n ‐C 6 F 13 CH 2 CH 2 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 ‐C 6 F 13 CH 2 CH 2 esters up to 81 and 70 %, respectively. The reaction with deuterated starting materials acetone‐ d 6 and MeOH‐ d 4 , with DBU in acetonitrile afforded deuterated MMA (MMA‐ d 8 ) in 70 % yield.