Synthesis and thermal decomposition of N,N-dialkoxyamides

Author(s)
Digianantonio, Katherine M
Glover, Stephen
Johns, Jennifer
Rosser, Adam Andrew
Publication Date
2011
Abstract
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 ¹³C 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.
Citation
Organic & Biomolecular Chemistry, 9(11), p. 4116-4126
ISSN
1477-0539
1477-0520
Link
Publisher
Royal Society of Chemistry
Title
Synthesis and thermal decomposition of N,N-dialkoxyamides
Type of document
Journal Article
Entity Type
Publication

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