Synthesis of Sulfated Acetamido Group-Containing Copolyribose by Selective Ring-Opening Polymerization and Chemical Modifications.

• Borjihan Gereltu

  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

抄録

Synthesis and sulfation of an acetamido group-containing copolyribose was carried out by a five-step synthetic route. Firstly, selective ring-opening copolymerization of 1, 4-anhydro-3-azido-2-O-t-butyldimethylsilyl (TBDMS)-3-deoxy-α-D-ribopyranose (A3ASR) and 1, 4-anhydro-2, 3-di-O-TBDMS-α-D-ribopyranose (ADSR) with BF₃•OEt₂ as a catalyst at low temperature produced an azido group-containing copolyribose, i.e., poly [ 3-azido-2-O-TBDMS-3-deoxy-(1→5)-α-ribofuranose-co-2, 3-di-O-TBDMS-(1→5)-α-ribofuranose] [copoly (A3ASR)]. The number-average molecular weight (_??__n) of the azido group-containing copolyriboses was in a range of 1.17×10⁴ to 2.96×10⁴. The specific rotation ([α]²⁰_D) increased from +117° to +204° as the mole fractions (%) of azido group-containing units (A3ASR) in the copolymers decreased from 83% to 16%. The reactivity ratios of A3ASR (r₁=0.42) and ADSR (r₂=1.16) in the ring-opening copolymerizations were estimated according to the Kelen-Tudos method.<br>Then, the azido group in a copoly (3A3ASR-ADSR) (_??__n of 1.11×10⁴ and [α] ²⁰_D of +141.6°) was reduced into amino group with NaBH4 in a mixture of THF-ethanol to afford an amino group-containing copolymer, i.e., poly [3-amino-2-O-TBDMS-3-deoxy-(1→5)-α-ribofuranose-co-2, 3-di-O-TBDMS-(1→5)-α-ribofuranose] [copoly (AAmSR-ADSR)], and subsequent acetylation of the amino group with acetyl chloride gave an intermediate acetamido group-containing copolymer, i.e., poly [ 3-acetamido-2-O-TBDMS-3-deoxy-(1→5)-α-ribofuranose-co-2, 3-di-O-TBDMS-(1→5)-α-ribofuranose] [copoly (A3AAdSR-ADSR)], and then de-t-butyldimethylsilylation of the copolymer produced a water-soluble acetamido group-containing copolyribose, i.e., poly [ 3-acetamido-3-deoxy-(1→5)-α-ribofuranose-co-(1→5)-α-ribofuranose] [copoly (A3AAdR-R)] with _??__n of 8.63×10³ and [α]²⁰_D of +141.0°.<br>Finally, sulfation of the acetamido group-containing copolyribose [copoly (A3AAdR-R)] with a sulfur trioxide-pyridine complex in a mixture of dimethyl sulfoxide (DMSO) and pyridine produced a sulfated acetamido group-containing copolyribose [copoly (SA3AAdR-SR)] with _??__n of 10.68×10³ and [α] ²⁰_D of + 84.9°. The structures of acetamido group-containing copolymer and its sulfate were determined by ¹³C NMR. The degree of sulfation (DS=1.2) was measured by elemental analysis.

収録刊行物

• 繊維学会誌

  繊維学会誌 55 (4), 172-178, 1999

  社団法人 繊維学会

キーワード

• General Medicine

詳細情報

• CRID: 1390282679805798784
• NII論文ID: 130004206189
• NII論文ID: 10002061736
• NII書誌ID: AN00131651
• DOI: 10.2115/fiber.55.4_172
• ISSN: 18842259
• ISSN: 00379875
• NDL書誌ID: 4701317
• Web Site: https://ndlsearch.ndl.go.jp/books/R000000004-I4701317
• Web Site: http://www.jstage.jst.go.jp/article/fiber1944/55/4/55_4_172/_pdf
• 本文言語コード: en
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