Safety Assessment of Diels–Alder Reactions with Highly Reactive Acrylic Monomers

The Diels–Alder reactions of the diene (cyclohexa-1,5-dien-1-yloxy)trimethylsilane with either of the two dienophiles α-acetoxyacrylonitrile or α-chloroacrylonitrile pose severe safety hazards for scale-up. We report the systematic thermal hazard assessment of these Diels–Alder reactions and discuss...

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Bibliographic Details
Published in:Organic process research & development 2012-12, Vol.16 (12), p.2015-2020
Main Authors: Abele, Stefan, Schwaninger, Mischa, Fierz, Hans, Schmidt, Gunther, Funel, Jacques-Alexis, Stoessel, Francis
Format: Article
Language:English
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Summary:The Diels–Alder reactions of the diene (cyclohexa-1,5-dien-1-yloxy)trimethylsilane with either of the two dienophiles α-acetoxyacrylonitrile or α-chloroacrylonitrile pose severe safety hazards for scale-up. We report the systematic thermal hazard assessment of these Diels–Alder reactions and discuss their classification according to the Stoessel criticality diagram. Whereas the use of α-acetoxyacrylonitrile is not recommended, the reaction of the diene with α-chloroacrylonitrile can be scaled up when running the reaction in toluene in the presence of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) and sodium bicarbonate.
ISSN:1083-6160
1520-586X
DOI:10.1021/op300145k