Ring-Opening Polymerization of 1, 4-Anhydro-3-azido-3-deoxy-2-<i>O</i>-(<i>p</i>-substituted benzyl)-α-D-ribopyranoses

• Borjihan Gereltu

  Institute of Industrial Science, University of Tokyo

• Matsumura Yoshiyuki

  Institute of Industrial Science, University of Tokyo

• Katsuraya Kaname

  Institute of Industrial Science, University of Tokyo

• Uryu Toshiyuki

  Institute of Industrial Science, University of Tokyo

Bibliographic Information

Other Title

• Ring-Opening Polymerization of 1,4-Anhydro-3-azido-3-deoxy-2-O-(p-substituted benzyl)-α-D-ribopyranoses
• Ring-Opening Polymerization of 1,4-Anhydro-3-azido-3-deoxy-2-O- p-substituted benzyl-アルファーD-ribopyranoses

Abstract

A new series of 1, 4-anhydro-3-azido-ribopyranose derivatives was synthesized as functional monomers in order to study effects of the monomer structure on selective ring-opening polymerization behaviors and structures of the resulting polysaccharides. The general formula of the four monomers were written as 1, 4-anhydro-3-azido-3-deoxy-2.O-(p-substituted benzyl)-α-D-ribopyranose (A3A2SBR), in which the substituted group represented methyl (CH₃), hydrogen (H), chloro (CI), and bromo (Br) group. The four monomers were synthesized by reaction of 1, 4-anhydro-3-azido-3-deoxy-2-O-acetyl-α-D-ribopyranose with p-substituted benzyl chlorides or bromides. Selective ring-opening polymerization of the monomers was performed by BF₃•OEt₂ catalyst at -20°_??_40°C to give 3-azido-3-deoxy-2-O-(p-substituted benzyl)-(1→5)-α-D-ribofuranans with _??__n of 1.7×10⁴_??_4.6×10⁴and[α]_D²⁰of+180.1_??_+217.2°. Ring-opening polymerization by SbCl₅ catalyst at-40°C afforded a polymer composed of a mixture of 1, 5-α-and 1, 5-β-ribofuranosidic units. In the selective ring-opening polymerization by BF₃•OEt₂ catalyst, _??__n increased and molecular weight distributions _??__n/_??__w became narrower with changing Hammett sigma constant of the p-substituted groups from negative to positive values in following order: methyl (-1.4), hydrogen (0), chloro (+2.4) and bromo (+2.6) groups. It was revealed that the p-substituted groups with different Hammett sigma constants had a regular effect in the ring-opening polymerization.

Journal

• Sen'i Gakkaishi

  Sen'i Gakkaishi 55 (5), 208-217, 1999

  The Society of Fiber Science and Technology, Japan

Keywords

• General Medicine

Details

• CRID: 1390001204895126400
• NII Article ID: 130004206206
• NII Article ID: 10002061862
• NII Book ID: AN00131651
• DOI: 10.2115/fiber.55.5_208
• ISSN: 18842259
• ISSN: 00379875
• NDL BIB ID: 4733878
• Web Site: https://ndlsearch.ndl.go.jp/books/R000000004-I4733878
• Web Site: http://www.jstage.jst.go.jp/article/fiber1944/55/5/55_5_208/_pdf
• Text Lang: en
• Data Source:
  • JaLC
  • NDL
  • Crossref
  • CiNii Articles
• Abstract License Flag: Disallowed