Molecular design and utilization of hybid-functional cellulose derivatives

杂化功能纤维素衍生物的分子设计与利用

• 批准号: 11556031
• 负责人: NAKATSUBO Fumiaki
• 金额: $ 8.7万
• 依托单位: KYOTO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-11556031/
• 关键词: hybrid-functional cellulose derivatives; 4-alkyloxytrityl chiorides; solubility; liquid crystalline property; ring-opening polymerization; 3-O-Allyl group; regioselectively-methylated celluloses; magnetism or electro-conductivity; ハイブリッド機能セルロース誘導体

The structural feature of cellulose molecule is to have three hydroxyl groupsin the repeating anhydro glucose unit. Considering the reactivity of these hydroxyl groups enable us to open interesting possibilities to design advanced cellulose derivatives with multiple functions in the single molecule.We planned to preare a hybrid-functional cellulose derivatives with long chain alkyl group at 6-0-position expecting the improved solubility and thermal property, and special functions at 2- and 3-0-positions. The results are as follows:1) Nobel etherification reagents,4-alkyloxytrityl chlorides with different alkyl chain lengths which regioselectively reacts with 6-0-psition of cellulsoe, were synthesized from commercial methyl benzoate or p-hydroxybenzophenone via a key intermediate, 4-hydroxytrityl alcohol.2) The novel reagents were found to react regioselectively with 6-O-position of methyl a-D-glucose orcellulose. The obtained, cellulose derivatives showed improved solubility and melted with liquid crystalline property.3) The synthetic method of ring-opening polymerization monomer for preparing cellulose was improved to give.Higher overall yields with fewer reaction steps. 3-O-AllyI group of the monomer was indicated to be more useful than benzyl group from the synthetic point of view.4) All possible 7 regioselectively-methylated celluloses were prepared from the ring-opening polymerization products. Thus, the method can be applied for the preparation of regioselectivly-substituted cellulose derivatives with long chain, which may be converted hybrid-functional cellulose derivatives with magnetism or electro-conductivity.

纤维素分子的结构特征是在重复的无水葡萄糖单元中有三个羟基。考虑到这些羟基的反应性，我们可以在单分子中设计出具有多种功能的高级纤维素衍生物。我们计划制备具有6-0位长链烷基的杂化功能纤维素衍生物，期望其溶解度和热性能得到改善，并且在2-和3-0位具有特殊功能。结果表明：1)以工业苯甲酸甲酯或对羟基二苯甲酮为原料，以关键中间体4-羟基三醇为原料，合成了具有不同烷基链长度的与纤维素6-0位发生区域选择性反应的诺贝尔醚化试剂4-烷基氧基三酰氯。2)发现新试剂与甲基a- d -葡萄糖或纤维素的6- o位有区域选择性反应。所得纤维素衍生物的溶解度提高，熔融时具有液晶性质。3)改进了制备纤维素用开环聚合单体的合成方法。反应步骤少，总产率高。从合成的角度来看，该单体的3- o - alli基团比苄基更有用。4)由开环聚合产物制备了所有可能的7种区域选择性甲基化纤维素。因此，该方法可用于制备具有长链的区域选择性取代的纤维素衍生物，该衍生物可转化为具有磁性或导电性的混合功能纤维素衍生物。

项目成果

Makoto Karakawa and Fumiakl Nakatsubo: "An improved synthetic method for 3-O-benzyl-6-Opivaloyl-α-D-glucopyranose1,2,4-orthopivalate, the starting monomer for synthetic cellulose by a catiohic ring-opening polymerization"Carbohydrate Research. (in press).

Makoto Karakawa 和 Fumiakl Nakatsubo：“通过阳离子开环聚合合成纤维素的起始单体 3-O-benzyl-6-Opivaloyl-α-D-glucopyranose1,2,4-ortovalate 的改进合成方法”碳水化合物研究（在新闻）。

Makoto Karakawa, Hiroshi Kamitakahara, Toshiyuki Takano Fumiaki Nakatsubo: "The Utility of a 3-O-Allyl Group as a Protective Group for fling-Opening Polymerization of α-D-Glucopyranose 1, 2, 4-Orthopivalate Derivatives"Blomacromolecules. (in press).

Makoto Karakawa、Hiroshi Kamitakahara、Toshiyuki Takano Fumiaki Nakatsubo：“3-O-烯丙基作为保护基团用于 α-D-吡喃葡萄糖 1, 2, 4-Ortovalate 衍生物的快速开放聚合”Blomamoleculecros Press）。 。

M.Karakawa, H.Kamitakahara, T.Takano, F.Bakatsubo: ""The Utility of a 3-O-Allyl Group as a Protective Group forRing-Opening Polymerization of α-D-Glucopyranose 1,2,4-Orthopivalate Derivatives"Biomacromolecules. (in press).

M.Karakawa、H.Kamitakahara、T.Takano、F.Bakatsubo：“3-O-烯丙基作为保护基在 α-D-吡喃葡萄糖 1,2,4-原戊酸衍生物开环聚合中的应用“生物大分子。（正在出版）。

M.Karakawa, F.Nakatsubo: ""An Improved synthetic method for 3-O-benzyl-6-O-pivaloyl-α-D-glucopyranose 1,2,4-orthopivalate, the starting monomer for synthetic cellulose by a cationic ring-opening polymerization""Carbohydrate Research. (in press).

M.Karakawa、F.Nakatsubo：“一种改进的 3-O-苄基-6-O-新戊酰基-α-D-吡喃葡萄糖 1,2,4-原戊酸的合成方法，通过阳离子环合成纤维素的起始单体-开放聚合”“碳水化合物研究（正在出版）。

Hori,M.and Nakatsubo F.: "Substituent effect of the C6-position on ring-opening polymerization of glucose ortho esters^* Synthesis of stereoregular 6-deoxy-(1→4)-β-D-glucopyranan"Macromolelecules. (2001)

Hori, M. 和 Nakatsubo F.：“C6 位对葡萄糖原酸酯开环聚合的取代效应^* 立构规整 6-脱氧-(1→4)-β-D-吡喃葡萄糖的合成”大分子（ 2001）