SYNTHESIS OF POLY[(1-]6)-2,5-ANHYDRO-D-GLUCITOL] BY CATIONIC CYCLOPOLYMERIZATION OF 3,4-DI-O-ALLYL-1,2 5,6-DIANHYDRO-D-MANNITOL/

The cyclopolymerization of 3,4-di-O-allyl-1,2:5,6-dianhydro-D-mannitol (1d) using BF3 . OEt(2) produced oly[(1-->6)-3,4-di-O-allyl-2,5-anhyd ro-D-glucitol] (2d). For the polymerization in CH2Cl2 at -10 degrees C , the maximum yield and Mn were obtained as 58.9% and 4890, respective ly. The specific rotations ([alpha](22)546) of the obtained polymers w ere +34.0 degrees similar to +38.8 degrees (c=1.0 in CHCl3). The deall ylation of polymer 2d in acetic acid/ethanol/water using the Pd-C cata lyst perfectly proceeded to form poly[(1-->6)-2,5-anhydro-D-glucitol] (3). The specific rotations ([alpha](22)546) of the resulting polymers were +17.1 degrees similar to +18.9 degrees (c=1.0 in H2O). Polymer 2 d was soluble in chloroform and tetrahydrofuran, but insoluble in wate r, whereas polymer 3 was soluble in water but insoluble in chloroform and tetrahydrofuran.