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.

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-肯德罗-3-O-甲基辅助醇单位。此外，中己醇（1，2：2：2：5，6-二羟基3，4-di-o-甲基 - 丙醇）的环聚合产生了由5和6元的循环单元组成的聚合物，该聚合物使用阴离子和阳离子式启动器进行了回答。对于1、2：5、6-二羟基3、4-二二o-甲基 - 半乳酸，使用阴离子引发剂的聚合是正式和立体选择性的，而阳离子不是规则的。使用手性锌配合物的4-DI-O-甲基 - 半乳酸醇具有非映选择性，可提供由5元循环和无形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: "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)

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)

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)