Unusual reactivity of N-tert-butylimines under FVT conditions

• Published in: Tetrahedron Vol. 69; no. 2; pp. 722 - 729
• Main Authors: Leśniak, Stanisław, Pasternak, Beata, Justyna, Katarzyna, Vu, Thien Y., Xuan Huynh, Thi Kieu, Khayar, Saïd, Dargelos, Alain, Chrostowska, Anna
• Format: Journal Article
• Language: English
• Published: OXFORD Elsevier Ltd 14.01.2013; Elsevier
• Subjects: 2-Methylimidazole; Activation; Bonding; Chemical Sciences; Chemistry; Chemistry, Organic; Cleavage; Flash vacuum thermolysis; Formations; Inorganic chemistry; Organic chemistry; Photoelectron spectroscopy; Physical Sciences; Pyrroles; Radicals; Science & Technology; Spectroscopy; Tetrahedrons; Flash vacuum thermolysis; 2-Methylimidazole; Photoelectron spectroscopy; POLYAZAPENTADIENES; EXCITATION-ENERGIES; IONIZATION-POTENTIALS; APPROXIMATION; UV-PHOTOELECTRON SPECTROSCOPY; DECOMPOSITION; DENSITY-FUNCTIONAL THEORY; GAS-PHASE GENERATION; ELECTRONIC-STRUCTURE; Flash vacuum thermolysis Photoelectron spectroscopy 2-Methylimidazole
• ISSN: 0040-4020; 1464-5416
• DOI: 10.1016/j.tet.2012.10.090

Thermal reactions of N-tert-butyl-(E)-crotonaldimine (1a) and 1,4-di-(tert-butyl)-1,4-diazabuta-1,3-dien (glyoxal-bis-N-tert-butylimine) (1b) under FVT conditions have been studied. It has been found that at 800 °C compound 1a yielded pyrrole and crotononitrile, presumably via homolytic t-Bu–N bond cleavage and formation of the iminyl radical. In the reaction of 1b at 800 °C, 2-methylimidazole (4b) has been obtained unexpectedly as the major product. The mechanism of these reactions has been proposed. Furthermore, combined FVT and UV-photoelectron spectroscopy have been applied for direct generation and in situ characterization of compounds 1a and 1b under thermal activation conditions. [Display omitted]