Chemical syntheses of regiospecific substituted cellulose derivatives-solution for basic problem of cellulose chemistry

区域特异性取代纤维素衍生物的化学合成-解决纤维素化学的基本问题

• 批准号: 09460076
• 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: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09460076/
• 关键词: Chemical synthesis of cellulose; regiospecifically methylated cellulose; spectroscopic data; substituent distribution; carboxymethylation; methylation; reactivity of three hydroxyl groups; inter-and intramolecule hydrogen bondings; セルロース; 位置特異的置換

Since A. Payen named cellulose for natural fiber, cellulose research has been carried out for about 150 years. However, there are still several basic problems which should be solved : biosynthesis and biodegradation, crystal structure, mercelization mechanism, chemical reactivity, structure-function relationship.Recently, we have succeeded in the first chemical synthesis of cellulose both by stepwise method and by the ring-opening polymerization of glucose orthoester. These synthetic methods enables us to obtain the high-regioselectively substituted cellulose derivatives which can used for the solution of the above several basic problems. In the present investigation, We succeeded in the preparation of 6 regiospecifically methylated celluloses in the possible 7 methyl celluloses. Based on the spectroscopic data of these synthetic methyl celluloses, we established the determination method for the substituent distribution of methyl celluloses. As the results of carboxymethylation and methylation of celluose, we found the new findings about the reactivity of three hydroxyl groups in cellulose molecule. These results suggest new possible effects of inter- and intramolecule hydrogen bondings on the reactivity of three hydroxyl groups.

自从A. Payen将纤维素命名为天然纤维，纤维素的研究已经进行了约150年。然而，纤维素的生物合成与生物降解、晶体结构、矿化机理、化学反应性、结构与功能的关系等基本问题尚待解决。这些合成方法使我们能够获得高区域选择性取代的纤维素衍生物，可用于解决上述几个基本问题。在本研究中，我们成功地制备了可能的7种甲基纤维素中的6种区域特异性甲基化纤维素。根据这些合成甲基纤维素的光谱数据，建立了甲基纤维素取代基分布的测定方法。通过对纤维素的羧甲基化和甲基化反应，我们发现了纤维素分子中三个羟基的反应活性的新发现。这些结果表明，新的可能影响分子间和分子内氢键的反应性的三个羟基。

项目成果

中坪 文明: "The first chemical synthesis of cellulose and its future prospects" 10 th ISWPC Proceedings. (1999)

Fumiaki Nakatsubo：“纤维素的首次化学合成及其未来前景”第 10 届 ISWPC 会议记录（1999 年）。

三川裕司 等: "Chemical syntheses of regiospecific substituted methyl cellulose" J.Wood.Science. (1999)

Yuji Mikawa 等人：“区域特异性取代甲基纤维素的化学合成”J.Wood.Science (1999)。

Shigetomo Tsujihata,and Fumaiaki Nakatsubo: "A Novel Synthetic Method for α-D-galactofuranose 1,2,5-orthopivalate" Carbohydrate Research. (accepted).

Shigetomo Tsujihata 和 Fumaiaki Nakatsubo：“α-D-呋喃半乳糖 1,2,5-原戊酸的新合成方法”碳水化合物研究（已接受）。