Synthesis of the substituted and crosslinked glucoses corresponding to the structural units in a cotton cellulose modified with N-methylbis(2-chloroethyl)amine

Abstract

The syntheses of simple substituted glucoses (i.e., 2-O-, 3-O-, and 6-O-[(N-methyl-N-2-hydroxyethylamino)ethyl]-D-glucopyranoses) and simple crosslinked glucoses (i.e., N-methylaminobis[O-(N-2-ethyl)-D-glucopyranoses]) with glucose linkages at 2,2′-O-, 3,3′-O-, 6,6′-O-, 2,6′-O-, and 3,6′-O-positions are described. These result from the reactions of "blocked" glucoses with N-methylbis(2-chloroethyl)amine. The new derivatives were characterized by gas–liquid chromatography and electrophoresis. Cotton cellulose modified with N-methylbis(2-chloroethyl)amine to incorporate 0.034 mole of reagent per D-glucopyranosyl unit was hydrolyzed to glucose and substituted glucoses; the substituted glucoses were identified by chromatographic and electrophoretic comparisons with the foregoing authentic glucose derivatives. The relative distribution of (N-methyl-Nhydroxyethylamino)ethyl groups among the 2-O-, 3-O-, and 6-O-positions was 2.30:0.28:1.00. The distribution of crosslinkages among the 2,2′-O-, 2,6′-O-, and 6,6′-O-positions was 2.10:3.72:1.00; these are the only crosslinked derivatives found. The monofunctionally substituted fraction (having a single reagent unit in the substituent group) accounted for 42.6% of the nitrogen; the crosslinked fraction (having a single reagent unit in the crosslink) accounted for 25.8%; complex products accounted for the remainder of the nitrogen of the crosslinked cotton.