Synthesis and ring-opening polymerization of new 1,4-anhydro-glucopyranose derivatives

✍ Scribed by Takashi Yoshida; Kazuyuki Hattori; Yoonsoung Choi; Masataka Arai; Hiroyuki Funaoka; Toshiyuki Uryu

• Publisher: John Wiley and Sons
• Year: 1998
• Tongue: English
• Weight: 256 KB
• Volume: 36
• Category: Article
• ISSN: 0887-624X
• DOI: 10.1002/(sici)1099-0518(19980415)36:5<841::aid-pola17>3.0.co;2-g

✦ Synopsis

Three new 1,4-anhydro-glucopyranose derivatives having different hydroxyl protective groups such as 1,4-anhydro-2,3,6-tri-O-methyl-a-D-glucopyranose (AMGLU), 1,4-anhydro-6-O-benzyl-2,3-di-O-methyl-a-D-glucopyranose (A6BMG), and 1,4-anhydro-2,3-di-O-methyl-6-O-trityl-a-D-glucopyranose (A6TMG) were synthesized from methyl a-D-glucopyranoside in good yields. Their polymerizability was compared with that of 1,4-anhydro-2,3,6-tri-O-benzyl-a-D-glucopyranose (ABGLU) reported previously. The trimethylated monomer, AMGLU, was polymerized by a PF 5 catalyst to give 1,5-a-furanosidic polymer having number-average molecular weights (M V n ) in the range of 2.8 1 10 3 to 6.8 1 10 3 . The 13 C-NMR spectrum was compared with that of methylated amylose and cellulose. Other anhydro monomers, A6BMG and A6TMG, gave the corresponding 1,5-a furanosidic polymers having M V n Å 17.1 1 10 3 and 1.8 1 10 3 , respectively. Thus, the substituents at the C2 and C6 positions were found to play an important role for the ring-opening polymerizability of the 1,4-anhydro-glucose monomers. In addition, debenzylation of the tribenzylated polymer gave free (1 r 5)-a-D-glucofuranan.