4091-14-9Relevant articles and documents
N-Ethynylation of Anilides Decreases the Double-Bond Character of Amide Bond while Retaining trans-Conformation and Planarity
Yamasaki, Ryu,Morita, Kento,Iizumi, Hiromi,Ito, Ai,Fukuda, Kazuo,Okamoto, Iwao
supporting information, p. 10118 - 10122 (2019/07/05)
Activated amide bonds have been attracting intense attention; however, most of the studied moieties have twisted amide character. To add a new strategy to activate amide bonds while maintaining its planarity, we envisioned the introduction of an alkynyl group on the amide nitrogen to disrupt amide resonance by nN→Csp conjugation. In this context, the conformations and properties of N-ethynyl-substituted aromatic amides were investigated by DFT calculations, crystallography, and NMR spectroscopic analysis. In contrast to the cis conformational preference of N-ethyl- and vinyl-substituted acetanilides, N-ethynyl-substituted acetanilide favors the trans conformation in the crystal and in solution. It also has a decreased double bond character of the C(O)?N bond, without twisting of the amide. N-Ethynyl-substituted acetanilides undergo selective C(O)?N bond or N?C(sp) bond cleavage reactions and have potential applications as activated amides for coupling reactions or easily cleavable tethers.
INVESTIGATION OF THE STRUCTURES OF AND THE INTRAMOLECULAR INTERACTIONS IN N-VINYLAMIDES BY MEANS OF MULTINUCLEAR NMR SPECTROSCOPIC (1H, 13C, 15N, 17O) DATA AND THE RESULTS OF QUANTUM-CHEMICAL CALCULATIONS
Afonin, A. V.,Trofimov, B. A.,Malysheva, S. F.,Vashchenko, A. V.
, p. 181 - 190 (2007/10/02)
As a result of an analysis of the parameters of the 1H, 13C, 15N, and 17O NMR spectra of a number of N-vinylanilides it was established that the phenyl ring is orthogonal to the plane of the amido group, while the vinyl and carbonyl groups are coplanar.Th
