Using Desmotropes, Cocrystals, and Salts to Manipulate Reactivity in Mechanochemical Organic Reactions

Performing reactions in the solid state offers the largely unexplored possibility of influencing reactivity by manipulating the solid form of the starting reactants. In this work, we explore the use of various solid forms of barbituric acid and its effect on reaction paths and kinetics in a Knoevena...

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Bibliographic Details
Published in:Journal of organic chemistry 2021-10, Vol.86 (20), p.14160-14168
Main Authors: Kralj, Magdalena, Lukin, Stipe, Miletić, Goran, Halasz, Ivan
Format: Article
Language:English
Subjects:
condensation reactions
mechanochemistry
organic chemistry
reaction kinetics
reaction mechanisms
tautomers
vanillin
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Summary:Performing reactions in the solid state offers the largely unexplored possibility of influencing reactivity by manipulating the solid form of the starting reactants. In this work, we explore the use of various solid forms of barbituric acid and its effect on reaction paths and kinetics in a Knoevenagel condensation reaction with vanillin. Modifications of barbituric acid included the use of its desmotrope, a cocrystal, and a salt as the starting reactant. Comparing these reactions with the reaction starting from the commercial keto tautomer of barbituric acid, we find that the reaction kinetics could be accelerated or decelerated, together with a change in the reaction mechanism. Exploring solid forms of reactants can be used as general methodology for manipulating mechanochemical reactivity, further highlighting the benefits of conducting reactions in the solid state, because many of the modifications of solids become unavailable upon dissolution.
ISSN:0022-3263
1520-6904
1520-6904
DOI:10.1021/acs.joc.1c01817