Microwave-Specific Acceleration of a Friedel鈥揅rafts Reaction: Evidence for Selective Heating in Homogeneous Solution

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• 作者：Michael R. Rosana ; Jacob Hunt ; Anthony Ferrari ; Taylor A. Southworth ; Yuchuan Tao ; Albert E. Stiegman ; Gregory B. Dudley
• 刊名：Journal of Organic Chemistry
• 出版年：2014
• 出版时间：August 15, 2014
• 年：2014
• 卷：79
• 期：16
• 页码：7437-7450
• 全文大小：624K
• ISSN：1520-6904

文摘

Thermally promoted Friedel鈥揅rafts benzylation of arene solvents has been examined under both conventional convective heating with an oil bath and heating using microwave (MW) energy. Bulk solution temperatures鈥攁s measured by internal and external temperature probes and as defined by solvent reflux鈥攚ere comparable in both sets of experiments. MW-specific rate enhancements were documented under certain conditions and not others. The observed rate enhancements at a given temperature are proposed to arise from selective MW heating of polar solutes, perturbing thermal equilibrium between the solute and bulk solution. Central to MW-specific thermal phenomena is the difference between heat and temperature. Temperature is a measure of the ensemble average kinetic molecular energy of all solution components, but temperature does not provide information about solute-specific energy differences that may arise as a consequence of selective MW heating. Enhanced chemical reactivity of the MW-absorbing solute can be described as a MW-specific 鈥渆xtra-temperature thermal effect鈥? because the measurable solution temperature only captures a portion of the solute kinetic molecular energy. Experimental factors that favor MW-specific rate enhancements are discussed with an eye toward future development of MW-actuated organic reactions, in which the observed thermal reactivity exceeds what is predicted from temperature-based Arrhenius calculations.