Collect. Czech. Chem. Commun. 1991, 56, 2950-2963

The synthesis of 4-O-oligoethylene glycol derivatives of 1,6-anhydro-β-D-glucopyranose and crown-ethers formed by their intramolecular cyclization

Jindřich Jindřicha, Miloslav Černýb, Tomáš Trnkab and Miloš Buděšínskýa

a Institute of Organic Chemistry and Biochemistry, Czechoslovak Academy of Sciences, 166 10 Prague 6
b Department of Organic Chemistry, Charles University, 128 40 Prague 2


Using acid catalysed reaction of 1,6 : 3,4-dianhydro-2-O-p-toluenesulfonyl-β-D-galactopyranose (I) with mono-, di-, tri- and tetraethylene glycol, 4-O-oligoethylene glycol derivatives of 1,6-anhydro-2-O-p-toluenesulfonyl-β-D-glucopyranose II - V were obtained which were converted to 4-O-substituted 1,6 : 2,3-dianhydro-β-D-mannopyranones VI - IX under the effect of sodium hydroxide. Of them 4-O-(2-hydroxyethyl)- and 4-O-(11-hydroxy-3,6,9-trioxaundecyl) derivatives VI and IX were intramolecularly cyclized in basic medium under formation of 1,6-anhydro-3,4-O-ethlene-β-D-altropyranose (X) or 1,6-anhydro-2,4-O-(3,6,9-trioxaundecane-1,11-diyl)-β-D-glucopyranose (XV), respectively. Oxidation of the hydroxyl group in compound XV led to corresponding 3-ulose XIX, the reduction of which with sodium borohydride gave an isomer of compound XV, i.e. compound XX of D-allo-configuration. The structures of the compounds described in this paper were proved using 1H and 13C NMR spectra. Compounds XV, XIX and XX represent a new structural type of sugar crown-ethers.