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。新型硅烷酚的合成。遵循新的硅烷醇制备，分离，并确定其结构。硅烷二醇，RSI（OH）_3，disiloxanetetraols，（rsi（oh）_2O）_2（r = i-pr，mes，tip，tip，cyclohecyl）;环乙烯甲酚，（i-prsi（oh）o）_4（所有四个异构体）;不完全凝结的西塞斯奎良烷，T_3（OH）_3，T_4（OH）_2和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，顺式，trans，顺式 - （i-prsi（oh）o）_4.3。通过应用我们的新方法（逐步构造梯形），合成了第一个官能化的三环岩石氧烷和五边形梯氧烷。四苯基和四氢三环梯形和五边形梯硅氧烷的结构通过X射线晶体学确定。此外，与分离的非对映异构体的反应使得构建第一个七环和非囊性梯形的反应是可能的。

项目成果

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。

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, 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。

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-