Synthesis of Supramolecular Compounds and Novel Siloxanes Starting from Silanols

以硅烷醇为原料合成超分子化合物和新型硅氧烷

• 批准号: 12640510
• 负责人: UNNO Masafumi
• 金额: $ 1.41万
• 依托单位: Department of Applied Chemistry, Faculty of Engineering, Gunma University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-12640510/
• 关键词: laddersiloxanes; stereospecific synthesis; cyclic silanols; supramolecular aggregates; nano tube and wire; thermal stability; functional material; selective synthesis; シロキサン; シラノール; 超分子; 水素結合; ラダーシロキサ; 固体反応

1. Synthesis of novel silanols.Following novel silanols were prepared, isolated, and their structures were determined ; Silanetriols, RSi(OH)_3, Disiloxanetetraols, (RSi(OH)_2O)_2 (R=i-Pr, Mes, Tip, cyclohexyl) ; Cyclotetrasiloxanetetraol, (i-PrSi(OH)O)_4 (all four isomers) ; Incompletely condensed silsesquioxanes, T_3(OH)_3, T_4(OH)_2, and T_5(OH).2. Supramolecular aggregates composed of silanols.Co-crystallization or recrystallization from mixed solvent gave novel hydrogen-bonded supramolecular aggregates : all-cis-(i-PrSi(OH))_4 and i-Pr_2Si(OH)_2, cis,trans-(TipSi(OH)O)_3 from MeOH/THF, cis,trans,cis-(i- PrSi(OH)O)_4, cis, trans, cis-(i-PrSi(OH)O)_4.3. Synthesis of polycyclic laddersiloxanes.By applying our new method (stepwise construction of laddersiloxanes), the first functionalized tricyclic laddersiloxanes and pentacyclic laddersiloxane were synthesized. The structures of the Tetraphenyl and tetrahydroxyl tricyclic laddersiloxanes, and pentacyclic laddersiloxane were determined by X-ray crystallography. In addition, reaction with separated diastereomer made it possible to construct first heptcyclic and nonacyclic laddersiloxanes.

1.新型硅烷醇的合成：制备、分离并确定了以下新型硅烷醇：硅烷三醇，RSi（OH）_3，二硅氧烷四醇，（RSi（OH）_2O）_2（R=i-Pr，Mes，Tip，环己基）;环四硅氧烷四醇，（i-PrSi（OH）O）_4（所有四种异构体）;不完全缩合的倍半硅氧烷，T_3（OH）_3，T_4（OH）_2和T_5（OH）。通过共结晶或在混合溶剂中重结晶，得到了新型的氢键超分子聚集体：all-cis-（i-PrSi（OH））_4和i-Pr_2Si（OH）_2，cis，trans-（TipSi（OH）O）_3，cis，trans，cis-（i-PrSi（OH）O）_4，cis，trans，cis-（i-PrSi（OH）O）_4。多环梯形硅氧烷的合成：采用我们的新方法（梯形硅氧烷的逐步构建），首次合成了功能化的三环梯形硅氧烷和五环梯形硅氧烷。用X-射线衍射法测定了四苯基和四羟基三环梯形硅氧烷和五环梯形硅氧烷的结构。此外，与分离的非对映体的反应使得有可能构建第一个七环和九环梯形硅氧烷。

项目成果

Keiichi Yamada, Masafumi Unno, Kyoko Kobayashi, Hiroyuki Oku, Hatsuo Yamamura, Shuki Araki, Hideyuki Matsumoto, Ryoichi Katakai, and Masao Kawai: "Stereochemistry of Protected Omithine Side Chains of Gramicidin S Derivatives : X-ray Crystal Structure of t

Keiichi Yamada、Masafumi Unno、Kyoko Kobayashi、Hiroyuki Oku、Hatsuo Yamamura、Shuki Araki、Hideyuki Matsumoto、Ryoichi Katakai 和 Masao Kawai：“短杆菌肽 S 衍生物受保护的鸟氨酸侧链的立体化学：t 的 X 射线晶体结构

Masafumi Unno, Keisuke Negishi, and Hideyuki Matsumoto: "Extended Silapericyclynes"Chem. Lett.. 340-341 (2001)

Masafumi Unno、Keisuke Negishi 和 Hideyuki Matsumoto：“扩展的 Silapericyclynes”化学。

Masafumi Unno, Akiko Suto, Keisuke Takada, and Hideyuki Matsumoto: "Synthesis of Ladder and Cage Silsesquioxanes from 1,2,3,4-Tetrahydroxycyclotetrasiloxane"Bull. Chem. Soc. Jpn.. 73. 215-220 (2000)

Masafumi Unno、Akiko Suto、Keisuke Takada 和 Hideyuki Matsumoto：“从 1,2,3,4-四羟基环四硅氧烷合成梯形和笼形倍半硅氧烷”公牛。

K.Yamada, M.Unno, K.Kobayashi, H.Oku, H.Yamamura, S.Arai, H.Matsumoto, R.Katakai, M.Kawai: "Stereochemistry of Protected Ornithine Side Chains of Gramicidin S Derivatives : X-ray Crystal Structure of the Bis-Boc-tetra-N-methyl Derivatives of Gramicidin"J.

K.Yamada、M.Unno、K.Kobayashi、H.Oku、H.Yamamura、S.Arai、H.Matsumoto、R.Katakai、M.Kawai：“短杆菌肽 S 衍生物受保护鸟氨酸侧链的立体化学：X-

Masafumi Unno, Akiko Suto, Hideyuki Matsumoto: "Pentacyclic Laddersiloxane"J. Am. Chem. Soc.. (in press). (2002)

海野雅文、须藤明子、松本秀之：“五环梯硅氧烷”J。