The ring-opening and ring-forming polymerization of diepoxides and diepisulfides leading to novel carbohydrate

双环氧化物和二环硫化物的开环和成环聚合产生新型碳水化合物

• 批准号: 10450348
• 负责人: KAKUCHI Toyoji kazuaki
• 金额: $ 7.17万
• 依托单位: HOKKAIDO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B).
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-10450348/
• 关键词: Cyclopolymerization; Diahynydro pentitol; Diahnydro hexitol; Diastereoselective cyclopolymerization; L-Arabinitol; Xilitol; Allitol; Galactitol; ジエピスルフィド; 環化重合; 光学活性高分子; 5員環構造; 非環化構造; イオノフォア; D-マンニトール; D-アラビニトール; 液膜; 光学分割; アドニトール; キシリトー

The research aimed to establish the synthesis of novel polymers consisting of heterocyclic units by the ring-opening and ring-forming polymerization of bifunctional monomers, such as 1)the cyclopolymerization of chiral dianhyro pentitol, 2)the cyclopolymerization of meso diahnydro pentitol and meso diahnydro hexitol, and 3)the diastereoselective cyclopolymerization of meso diepisulfide.1)The cationic polymerization of the chiral dianhyro pentitol, 1, 2 : 4, 5-dianhydro-3-O-methyl-L-arabinitol was regeo-and stereoselective to form the organic solvent-soluble polymer consisting 1, 4-anydro-3-O-methyl-adonitol units.2)For meso-diepoxides, the cationic polymerization of 1, 2 : 4, 5-dianhydro-3-O-methyl-xilitol proceeded as well as the chiral dianhyro pentitol to produce the carbohydrate polymer consisting 1, 4-anydro-3-O-methyl-arabinitol units. In addition, the cyclopolymerization of a meso hexitol, 1, 2 : 5, 6-dianhydro-3, 4-di-O-methyl-allitol, produced the polymers consisting of the 5-and 6-membered cyclic units using anionic and cationic initiators, respoctively. For 1, 2 : 5, 6-dianhydro-3, 4-di O-methyl-galactitol, the polymerization using the anionic initiator was regeo-and stereoselective, whereas the cationic one was not regular.3)The polymerization of a meso-diepisulfide, which was synthesized from 1, 2 : 5, 6-dianhydro-3, 4-di-O-methyl-galactitol, using the chiral zinc complex was diastereoselective to afford the chiral polymer consisting of the 5-membered cyclic and uncyclic units.

本研究旨在通过双功能单体的开环成环聚合合成由杂环单元组成的新型聚合物，如1）手性二氢戊醇的环聚，2）内消旋二氢戊醇和内消旋二氢戊醇的环聚己糖醇，3）内消旋二环硫醚的非对映选择性环聚。1）手性化合物的阳离子聚合二氢戊醇, 1, 2 : 4, 5-二脱水-3-O-甲基-L-阿拉伯糖醇具有区域和立体选择性，形成由 1, 4-脱水-3-O-甲基-阿东醇单元组成的有机溶剂可溶性聚合物.2) 对于内消旋二环氧化物，1, 2 : 4, 5-二脱水-3-O-甲基-木糖醇的阳离子聚合反应如下进行以及手性二氢戊醇生成由 1, 4-anydro-3-O-甲基-阿拉伯糖醇单元组成的碳水化合物聚合物。此外，内消旋己糖醇，1, 2 : 5, 6-二脱水-3, 4-二-O-甲基-蒜醇的环化聚合，使用阴离子和阳离子产生了由 5 和 6 元环状单元组成的聚合物。分别为发起人。对于 1, 2 : 5, 6-二脱水-3, 4-二 O-甲基-半乳糖醇，使用阴离子引发剂的聚合是区域选择性和立体选择性的，而阳离子引发剂则不是规则的。 3) 内消旋聚合二环硫醚是由 1, 2 : 5, 6-二脱水-3, 4-二-O-甲基-半乳糖醇，使用手性锌配合物合成的非对映选择性提供由5元环状和非环状单元组成的手性聚合物。

项目成果

T.Hatakeyama: "“Living" nature in anionic cyclopolymerization of 1,2:5,6-dianhydro-3,4-di-O-methyl-D-mannitol using potassium tert-butoxide/18-crown-6 initiating system" Macromolecules. 2889-2893 (1998)

T.Hatakeyama：“使用叔丁醇钾/18-crown-6引发体系进行1,2:5,6-二脱水-3,4-二-O-甲基-D-甘露醇阴离子环聚合的“活性”性质”高分子。2889-2893（1998）

T.Satoh, D.Kitazawa, R.Nonokawa, M.Kamada, K.Yokota, H.Hashimoto and T.Kakuchi: "Cyclopolymerization of 1, 2 : 5, 6-Diepithio-3, 4-di O-methyl-1, 2, 5, 6-tetradeoxy-D-mannitol and-L-iditol Leading to a Novel Thio-Sugar"Macromolecules. 33. 5303-5307 (2000)

T.Satoh、D.Kitazawa、R.Nonokawa、M.Kamada、K.Yokota、H.Hashimoto 和 T.Kakuchi：“1, 2 : 5, 6-Diepithio-3, 4-di O-methyl- 的环聚合

T.Kakuchi: "Macromolecular ionophore. 2. Metal cation-binding property of (1→6)-2,5-anhydro-D-glucitol"Polymer Journal. 31. 293-295 (1999)

T.Kakuchi：“高分子离子载体。2. (1→6)-2,5-脱水-D-葡萄糖醇的金属阳离子结合特性”聚合物杂志 31. 293-295 (1999)

T.Kakuchi: "Cationic ring-opening polymeriztion of 1,6-anhydro-2,3,4-tri-O-allyl-β-D-glucopyranose as a convenient synthesis of dextran"Macromol. Rapid Comun.. 21. 1003-1006 (2000)

T.Kakuchi：“1,6-脱水-2,3,4-三-O-烯丙基-β-D-吡喃葡萄糖的阳离子开环聚合作为葡聚糖的便捷合成”Macromol. 21. 1003 -1006 (2000)

S.Umeda: "A novel chiral stational phase in HPLC. Optical resolution of racemic amino compounds by (1→6)-2,5-anhydro-3,4-di-O-ethyl-D-glucitol bound on silica gel"Enantiomer. 5. 473-479 (2000)

S.Umeda：“HPLC 中的一种新型手性固定相。通过 (1→6)-2,5-脱水-3,4-二-O-乙基-D-葡萄糖醇结合在硅胶上光学拆分外消旋氨基化合物”对映体。5.473-479(2000)