Synthesis, reactions and theoretical studies of[1,2,4]triazolo[4,3-c]pyrimidinium- and[1,2,4]triazolo[4,3-a]pyrazinium-3-aminides
1997
[1,2,4]Triazolo[4,3-c]pyrimidinium-3-aminides 5a–h
have been synthesised by treating pyrimidin-6-yl thiosemicarbazide
derivatives 7f–n with dicyclohexylcarbodiimide (DCC). The above
aminides 5a–h were slowly hydrolysed in water but very rapidly
hydrolysed in 5 M aqueous hydrochloric acid to give
substituted 1,2,4-triazole derivatives (e.g.
5a,d,g → 8e,a,f, respectively); related
nucleophilic ring-opening reactions occurred when the aminides (cf.
5a–h) were treated with (separately) methanol and ethanol
(e.g. 5d → 8c and 8d, respectively). A
series of analogous [1,2,4]triazolo[4,3-a]pyrazinium-3-aminides
6a–e was prepared following the procedures described above. The
pyrazinium aminides 6 are stable in aq. 2 M HCl, and a stable
hydrochloride salt 13 was formed from one such substrate 6a.The structure and electronic properties of condensed triazolium
betaines 1, 5d, 6a and 15 have been studied using the semi-empirical
PM3/COSMO method and with the ab initio 6-31 basis set; the
implications of these results in respect of the potential of such
betaines for molecular rearrangement are discussed.
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