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Aminolysis of sucrose. VIII. Formation mechanism of heterocyclic compounds

I. Ježo and I. Lužák

Slovak Academy of Sciences, Bratislava 9

Abstract: cf. CA 64, 8277c. The reaction of aq. sucrose solns. with NH3 in an autoclave at 140° and 220° was studied by paper chromatography. In addn. to the homologs of pyrazine and imidazole, 2-methyl-, 2,5-dimethyl-, and 2,6-dimethylpyrazine and 4(5)-methyl-, and 4(5)-hydroxymethylimidazole, the presence of 2-methyl-5-(D-arabino-tetrahydroxybutyl)pyrazine, m. 198-200° (abs. EtOH), [α]23D -60.8° (c 1, H₂O), Rf 0.53; 2-methyl-6-(D-arabino-tetrahydroxybutyl)pyrazine, m. 169-70° (abs. EtOH), [α]23D -68° (c 1, H₂O), Rf 0.55; 2-methyl-5-(D-arabino-tetrahydroxybutyl)-3-(D-erythro-trihydroxypropyl)pyrazine, m. 151-2° (abs. EtOH), [α]23D -100° (c 1, H₂O), Rf 0.495; 4(5)-(D-arabino-tetrahydroxybutyl)imidazole, m. 162-3° (H₂O), [α]23D -18.7° (c 1, H₂O), Rf 01346; 2,5-bis(D-arabino-tetrahydroxybutyl)pyrazine, m. 234-5° (abs. EtOH), [α]23D -74.8° (c 1, H2O), Rf 0.243; 2-amino-2-deoxy-D-glucose, m. 129-32° (abs. EtOH), [α]23D 93° (c 1, CHCl₃), Rf 0.153, and a compd. of the general compn. C₁₂H₂₃NO₁₀(?), m. 85-7.5° (abs. MeOH), [α]23D 41.8° (c 1, CHCl₃), Rf 0.114, were detd. It was detd. that by increasing temp. up to 220°, there is an increase in the pyrazine and imidazole fractions with a simultaneous decrease of the polyhydroxyalkyl derivs. of the heterocyclic compds. indicating a thermal cleavage of the side chains. Contrary to the reports in the literature, the formation of the imidazole derivs. is not dependent on the presence of the catalysts and CH₂O (Parrod, CA 25, 3968) and on the presence of the fragmentation products of the sucrose (Windaus and Langenbeck, CA 17, 2884).

Full paper in Portable Document Format: 208a586.pdf (in Slovak)

Chemical Papers 20 (8) 586–594 (1966)