N-Tolylglycosylamines were synthesized from o-, m-, and p-toluidines and aldoses (D-glucose, D-galactose, D-mannose, L-rhamnose, D-xylose, and L-arabinose). The anomeric and isomeric compositions of the synthesized products were established using 13 C NMR methods.Toluidines characteristically have high physiological activity [1,2]. One of the possible cellular metabolic pathways of toluidines is their N-glycosylation, as a result of which the activity is considerably changed [3]. The N-glycosylation products of toluidines have been investigated. Their anomers were identified using PMR and gamma-resonance spectroscopy [4,5]. 13 C NMR spectroscopy made it possible to study the rotational isomerism around the N-glycoside bonds. The principal parameter of 13 C NMR spectroscopy is the chemical shift, which provides important information about the conformation [6]. Our goal was to investigate the N-glycosylation of o-, m-, and p-toluidines by aldoses (D-glucose, D-galactose, D-mannose, L-rhamnose, D-xylose, and L-arabinose) and to study the anomeric and isomeric compositions of the synthesized products using 13 C NMR methods.Of all methods for preparing N-glycosides with aromatic aglycons (direct reaction of sugars and amines, synthesis from derivatives of sugars and amines, trans-glycosylation), direct synthesis by reaction of unsubstituted monosaccharides and aromatic amines of moderate basicity (pK a 1-6) is a convenient method for preparing these compounds [7][8][9]. The pK a values for o-, m-, and p-toluidines are 4.39, 4.60, and 5.12, respectively. It is known that the yield of the target N-glycoside is strongly influenced by the basicity of the starting amine. The higher the basicity of the amine is, the easier the resulting N-glycoside undergoes various transformations (hydrolysis, Amadori-Heyns rearrangement, melanoidine formation, etc.) [10]. As a result, the preparative yield of the target N-glycoside decreases as the basicity of the starting amine increases. We selected the optimum conditions for the N-glycosylation considering the properties of the amine involved. This made it possible to isolate quantitatively the target products from the reaction mixtures. After the appropriate workup (recrystallization, paper chromatography and thin-layer chromatography over silica gel) and identification (melting point, IR spectrum, elemental analysis), the synthesized N-glycosides were investigated using 13 C NMR spectra.