Reactions of 1,4-bis[(S) methylbenzyl]-1,4-diazabutadiene (1), 1,4-bis[(R) 1′-chlorobutan-2′-yl]-1,4-diazabutadiene (2), 1,4-bis[(S,S) 1′-chloro-1′-phenyl-propan-2′-yl]-1,4-diazabutadiene (3), and 1,4-di-tert-butyl-1,4-diazabutadiene (4) with aluminum and indium halides were performed. Reaction of 1,4-diazabutadienes 1–4 with two equivalents of aluminum halides in toluene afforded ionic aluminum coordination compounds (5–10) which in THF solution are transformed into 1,3-dialkyl-2-methaneiminealkyl imidazolium heterocycles (11–14) by condensation of two 1,4-diazabutadienes and elimination of amine hydrochloride. Equimolar reactions of 1–4 with InCl3 in dry acetonitrile at −78 °C afforded the neutral and diamagnetic InCl3 coordination compounds (15–18), which are stable in the solid state under dry conditions, but in THF solution are slowly transformed into the corresponding 1,3-dialkyl-imidazolium heterocycles 19–22. The X-ray diffraction analyses of compounds 2, 3, 10, 11, 14 and 17 are described. Quantum mechanical calculations were performed in order to find the minimum energy conformers of 1,4-diazabutadienes, 1,3-dialkyl-2-methaneiminealkyl imidazolium and 1,3-dialkyl-imidazolium derivatives as well as the aluminum and indium coordination compounds.

The structure and reactivity of a series of new ethylaminedithiazinanes and bis‐diethylaminedithiazinanes synthesized from formaldehyde, NaSH, and N,N‐dimethyl‐ethylene‐diamine (1), N‐methyl‐ethylene‐diamine (2), and N‐ethyl‐ethylene‐diamine (3) are reported. Compound 1 afforded 2‐([1,3,5]‐dithiazinan‐5‐yl)‐ethylene‐N,N‐dimethyl‐amine (4). The reaction of 4 with dry CH₂Cl₂ gave N‐{2‐([1,3,5]dithiazinan‐5‐yl)‐ethylene}‐N‐chloromethyl‐N,N‐dimethyl‐ammonium chloride (5) in high yield, whereas in wet CH₂Cl₂ and DMSO provided a mixture of 5 with N‐{2‐([1,3,5]‐dithiazinan‐5‐yl)‐ethylene}‐N,N‐dimethyl‐ammonium hydrochloride (6).bis‐{2‐([1,3,5]‐Dithiazinan‐5‐yl)‐ethylene‐N‐alkyl‐amino}‐methylene‐disulfides (7) and (8) formed by two dithiazinanes linked through the chain (CH₂)₂NRCH₂SSCH₂NR(CH₂)₂‐ (7 R = methyl, 8 R = ethyl) reacted with CH₂Cl₂ giving after neutralization of the hydrolysis products the ethylaminedithiazinanes with different pendant N‐groups [(CH₂)₂NMeH₂⁺(9); (CH₂)₂NEtH₂⁺ (10); (CH₂)₂NMeH (11); (CH₂)₂NEtH (12); (CH₂)₂NMeHBH₃ (13) (CH₂)₂NEtHBH₃ (14). (CH₂)₂NMe₂BH₃ (15), and (CH₂)₂NEtMeBH₃.(16)]. The x‐ray diffraction analyses of compounds 5, 6, 9, and 10 are reported. Variable temperature NMR experiments afforded the Δ G^≠ of the ring interconversion of the six‐membered heterocycles 6, 9, and 10. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 22:59–71, 2011; View this article online at wileyonlinelibrary.com. DOI 10.1002/hc.20657