A series of aliphatic (C-4-C-12) diethers of methyl 4,6-0-cinnamylidene-alpha-D-glucopyranoside (1) were prepared as model compounds. Polycondensation of 1 and l,n-dibromoalkanes (2) catalyzed by K-2,CO3/KI or KOH/phase-transfer catalyst systems was performed in solvents (DMF/butyl acetate, DMSO). Reactions carried out in the presence of KOH/TBAC or KOH/18-crown-6 yield the complex mixture of products due to side reactions. IR, H-1 and C-13 NMR and ESI-MS were used to study the details of the polymer structure. (C) 2007 Elsevier Ltd. All rights reserved.