Synthesis and thermal decomposition of N,N-dialkoxyamides
| Autor: | Stephen A. Glover, Katherine M. Digianantonio, Adam A. Rosser, Jennifer P. Johns |
|---|---|
| Rok vydání: | 2011 |
| Předmět: |
Anomer
Magnetic Resonance Spectroscopy Free Radicals Molecular Structure Radical Organic Chemistry Thermal decomposition Temperature Stereoisomerism Carbon-13 NMR Photochemistry Biochemistry Medicinal chemistry Amides Homolysis chemistry.chemical_compound chemistry Amide Alkoxy group Physical and Theoretical Chemistry Mesitylene |
| Zdroj: | Organicbiomolecular chemistry. 9(11) |
| ISSN: | 1477-0539 |
| Popis: | N,N-dialkoxyamides 1c, a virtually unstudied member of the new class of anomeric amides, amides bearing two electronegative atoms at nitrogen, have been synthesised in useful yields directly from hydroxamic esters using phenyliodine(III)bis(trifluoroacetate) (PIFA). Infrared carbonyl stretch frequencies and carbonyl (13)C NMR properties have been reported, which support strong inhibition of amide resonance in these amides. Their thermal decomposition reactions in mesitylene at 155 °C proceed by homolysis to form alkoxyamidyl and alkoxyl free radicals in preference to HERON rearrangements to esters. The reactions follow first-order kinetics and for a series of N,N-dimethoxy-4-substituted benzamides, activation energies of 125-135 kJ mol(-1) have been determined together with weakly negative entropies of activation. |
| Databáze: | OpenAIRE |
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