Amine exchange reactions of 3-tert-butyl-6-(methylsulfanyl)-1,2,3,4-tetrahydro-1,3,5-triazine hydroiodide with amino acids

Alkylation of cyclic mannich bases, derivatives of thiourea and simple amino acids

“…In all three cases corresponding ion associates VIb-VId were identified. In the first two cases we confirmed the formation of associates VIb, VIc by coincidence of spectral characteristics of the samples isolated from the reaction mixture of aminolysis with those of the samples of compounds VIb, VIc obtained earlier in [1] and (or) in this study by the above way. In the third case the formation of ionic associate VId is suggested by analogy and needs to be confirmed by X-ray diffraction data, but we have not succeeded yet to grow a single crystal required for the XRD study.…”

“…The salts VIIa, VIIb can be obtained in another way, in the reaction of the corresponding amino acid with the cyclic thiourea VIII in water that indicates the occurrence under these conditions of the reaction of amine exchange (transamination). A similar reaction between compound VIII iodomethylate and amino acids in water has been described earlier [1]. The driving force of amine exchange in these cases, in addition to protonation of tert-butylamine is, apparently, the fact that compound VIII and its iodomethylate bearing bulky substituents are less stable than compounds II and V, respectively, stabilized either by intramolecular hydrogen bonding and salt formation or by Coulomb interaction and ionic association, respectively.…”

“…It was found in [1] that in the 1 H NMR spectra of DMSO solutions of zwitter-ion Va and its ionic associate with tert-butilammonium iodide VIa there was a difference in positions of the signals of methyl and cyclic methylene groups, obviously due to ionic interactions in the associate. Similar difference occurs in the spectra of the solutions of zwitter-ion Vb and its ionic associate with tert-butylammonium iodide VIb as well as zwitter-ion Vc and its ionic associate with tert-butylammonium iodide VIc.…”

“…It was shown in [1] that 3-tert-butyl-6-(methylsulfanyl)-1,2,3,4-tetrahydro-1,3,5-triazine hydroiodide enters in the amine exchange reaction with glycine and β-alanine. In the case of glycine the final product of the exchange, [4-(methylsulfanyl)-5,6-dihydro-1,3,5-triaz-3-inium-1(2H)-yl] acetate, was isolated from the reaction mixture of transamination in the individual form.…”

“…From aqueous solutions of isothiuronium salts IIIa-IIIc mixed in equimolar ratio with tert-butylamine after complete evaporation of water the ion associates crystallized of the respective zwitter-ions Va-Vc and tert-butylammonium iodide, a kind of "quadrupole" VIa-VIc, which had been obtained earlier in the reaction of amine exchange (transamination) from the 3-tert-butyl-6-(methylsulfanyl)-1,2,3,4-tetrahydro-1,3,5-triazine hydroiodide and the corresponding amino acid in water [1].…”