title: Reaction of iminopropadienones with amines--formation of zwitterionic intermediates, ketenes, and ketenimines.
abstract: Five aryliminopropadienones 4a- d have been synthesized by flash vacuum thermolysis (FVT) by using two different precursors in each case. These compounds were deposited at 50 K at a pressure of ca. 10(-6) mbar together with three different nucleophiles, namely, trimethylamine (TMA), dimethylamine (DMA), and diethylamine (DEA), in order to study their reactions as neat solids during warm-up by FTIR spectroscopy. The reaction with TMA showed that a zwitterionic species (5 and/or 6) was formed in all the cases. With DMA and DEA, an alpha-oxoketenimine and/or an imidoylketene (7 and 8 or 9 and 10) was formed as the final product. In addition, several bands were observed, which can be assigned to zwitterionic intermediates (11 or 12). Optimized structures and vibrational spectra for all products were calculated at the B3LYP/6-31G(d) level of theory by using the polarizable continuum model (epsilon = 5).
authors.affiliation: Chemistry Building, School of Molecular and Microbial Sciences, The University of Queensland, Brisbane, Qld 4072, Australia.
authors.forename: Rakesh Naduvile
authors.initials: RN
authors.lastname: Veedu
authors.forename: Okanya J
authors.initials: OJ
authors.lastname: Kokas
authors.forename: Isabelle
authors.initials: I
authors.lastname: Couturier-Tamburelli
authors.forename: Rainer
authors.initials: R
authors.lastname: Koch
authors.forename: Jean-Pierre
authors.initials: JP
authors.lastname: Aycard
authors.forename: Fabien
authors.initials: F
authors.lastname: Borget
authors.forename: Curt
authors.initials: C
authors.lastname: Wentrup
mesh_terms: D000588:Amines / Q000737:chemistry*; D004048:Diethylamines / Q000737:chemistry; D004123:Dimethylamines / Q000737:chemistry; D005030:Ethylenes / Q000737:chemistry*; D007097:Imines / Q000737:chemistry*; D007659:Ketones / Q000737:chemistry*; D008744:Methylamines / Q000737:chemistry
chemical_list: D000588:Amines; D004048:Diethylamines; D004123:Dimethylamines; D005030:Ethylenes; D007097:Imines; D007659:Ketones; D008744:Methylamines; C034516:dimethylamine; C034281:diethylamine; C008223:ketene; C023336:trimethylamine