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• W2097960135 abstract "Angewandte Chemie recently published an unusual Essay by Prof. C. Oliver Kappe and co-workers entitled, “Microwave Effects in Organic Synthesis—Myth or Reality?” The major point of discussion is an Edge Article we published last year in the RSC journal Chemical Science entitled, “On the Rational Design of Microwave-Actuated Organic Reactions.” The Angewandte Essay is unusual in its inclusion of 38 pages of experimental details in the Supporting Information, 30 of which describe unpublished data from original experiments pertaining to our work. These data are interpreted as conflicting with our report. We reject their alternative interpretations of our experiments, and we discuss here how the new data from their experiments in fact align with our conclusions. In our article, we provided an example of a microwave (MW)-actuated reaction system, which we define as one for which MW irradiation provides a synthetic advantage over conventional heating at the same temperature. We designed an extreme reaction system—an ionic benzyl-transfer reagent in a nonpolar aromatic solvent—and subjected it to extreme conditions: constant MW irradiation at high power (300 W). Our design of this chemical system was predicated on the concept of selective heat storage in the domains existing around microwave-absorbing solutes in nonabsorbing media at fixed (and typically high) applied microwave powers. The design rationale aligns with an understanding of selective microwave heating obtained from fundamental dielectric relaxation studies carried out by Richert and Huang. In such a system, the selective absorption of microwave energy by the solute will result in localized energy in the solvation domain (i.e. effective temperature) that is higher than the surrounding medium. The solute then acts as a molecular radiator, transferring thermal energy to the bulk solution. If convective heat transfer out of the domains is slow compared to the build-up of thermal energy within the solute domains, then the thermal energy of the solute will exceed what would be predicted based on the measured temperature of the bulk solution. As an extension of that work, one can hypothesize that a microwave-absorbing reactant in a nonabsorbing medium can potentially realize product formation at rates in excess of what would be expected from conventional heating at the same measured bulk temperature. Indeed, we observed reactivity enhancements under MW heating compared to conventional oil-bath heating in a benzylation of [D10]pxylene (Figure 1)." @default.
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• W2097960135 date "2013-07-03" @default.
• W2097960135 modified "2023-10-01" @default.
• W2097960135 title "Correspondence on Microwave Effects in Organic Synthesis" @default.
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• W2097960135 doi "https://doi.org/10.1002/anie.201301539" @default.
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