Effects of Electronics, Aromaticity, and Solvent Polarity on the Rate of Azaquinone鈥揗ethide-Mediated Depolymerization of Aromatic Carbamate Oligomers

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• 作者：Jessica S. Robbins ; Kyle M. Schmid ; Scott T. Phillips
• 刊名：The Journal of Organic Chemistry
• 出版年：2013
• 出版时间：April 5, 2013
• 年：2013
• 卷：78
• 期：7
• 页码：3159-3169
• 全文大小：526K
• 年卷期：v.78,no.7(April 5, 2013)
• ISSN：1520-6904

文摘

This paper uses physical-organic studies on well-defined oligomers to establish design principles for creating aromatic poly(carbamates) that depolymerize from head-to-tail in low dielectric constant environments when exposed to specific applied signals. We show that either increasing electron density or decreasing the aromaticity of aromatic repeating units in poly(carbamates) increase the overall depolymerization rate. For example, a methoxybenzene-based repeating unit provides depolymerization rates that are 143脳 faster than oligomers that contain a benzene-based repeating unit. Furthermore, the rate of depolymerization in the methoxybenzene-based system is tolerant to low dielectric environments, whereas the benzene-based oligomers are not.