G.L.C.-M.S. of partially methylated and acetylated derivatives of 3-deoxyoctitols

Partially methylated and acetylated 3-deoxyoctitols were prepared from derivatives of 3-deoxy-d-manno-2-octulosonic acid (KDO), and identified as the d-glycero-d-talo and d-glycero-d-galacto isomers by g.l.c.-m.s. Mono- and oligosaccharide derivatives of KDO were subjected in sequence to methylation, carboxyl-reduction, hydrolysis, carbonyl-reduction, and acetylation to yield 1,2,6-tri-O-acetyl-3-deoxyoctitol derivatives. Carboxyl-reduction and then methylation gave the series of 2,6-di-O-acetyl derivatives. Oligosaccharides with KDO at the reducing end, e.g., β-d-ribofuranosyl-(1→7)-KDO, α-l-glycero-d-manno-heptopyranosyl-(1→5)-KDO, and α-KDOp-(2→4)-KDO, yielded, after carbonyl-reduction, methylation, carboxyl-reduction, hydrolysis, and acetylation, the 1,7-, 1,5-, and 1,4-di-O-acetyl derivatives, whereas remethylation after carboxyl-reduction gave the 7-, 5-, and 4-O-acetyl derivatives of 3-deoxyoctitol. General rules for the fragmentation of 3-deoxyoctitols during e.i.-m.s. were established.