Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
BCSJ Award Article
H-type Zeolite-Catalyzed 1,4-Addition of Benzene Derivatives to Labile Acrolein
Daijiro HayashiTomoyuki NarisawaYoichi MasuiMakoto Onaka
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Volume 89 (2016) Issue 4 Pages 460-471

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The 1,4-addition of benzene derivatives to acrolein is a straightforward way to synthesize 3-arylpropanals. A survey of acid catalysts for the 1,4-addition of methoxy-substituted benzenes to acrolein revealed that H-Beta and H-Y were the most suitable catalysts. We hypothesized three side-reactions: (1) the double 1,4-addition of acrolein to the starting benzene derivatives, (2) the Friedel–Crafts-type alkylation to the desired product, and (3) the self-polymerization of acrolein. The type (3) side-reaction was inhibited by two different methods which kept the concentration of acrolein low in the reaction mixture or in the zeolite pores. First, acrolein monomers were in situ generated through the gradual monomerization of an acrolein cyclic trimer. Second, using a reaction solvent lowered the acrolein concentration in the zeolite pores due to the competitive adsorption. We discovered that the content of monomeric acrolein in a solvent was closely related to the polarity of the solvent. Actually, both methods improved the yields for the 1,4-additions of 1,3-dimethoxybenzene to acrolein. Other electron-rich benzene derivatives, such as phenol and N,N-dimethylaniline, were also applicable to the 1,4-addition reactions.

1,4-Addition of benzene derivatives to acrolein catalyzed by H-type zeolite in the liquid phase is studied. Two methods, the slow generation of acrolein from its cyclic trimer and the competitive adsorption of a solvent are effective to suppress the self-polymerization of acrolein. Fullsize Image
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© 2016 The Chemical Society of Japan
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