1,3-bis(triethoxysilyl)propane | 60021-86-5

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: 1,3-bis(triethoxysilyl)propane
• 英文别名: 3,9-Dioxa-4,8-disilaundecane, 4,4,8,8-tetraethoxy-；triethoxy(3-triethoxysilylpropyl)silane
• CAS: 60021-86-5
• 化学式: C₁₅H₃₆O₆Si₂
• 分子量: 368.618
• InChiKey: PYOKTQVLKOAHRM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.47
• 重原子数：
  23
• 可旋转键数：
  16
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  55.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  1,3-bis(triethoxysilyl)propane 在 盐酸 、 水 作用下， 以 乙醇 为溶剂， 反应 120.0h， 以10.8%的产率得到1,3,7,9-Tetraethoxy-2,8,13,14-tetraoxa-1,3,7,9-tetrasila-tricyclo[7.3.1.1^3,7]tetradecane
  参考文献：
  名称：

  Cyclization Phenomena in the Sol−Gel Polymerization of α,ω-Bis(triethoxysilyl)alkanes and Incorporation of the Cyclic Structures into Network Silsesquioxane Polymers

  摘要：

  Intramolecular cyclizations during acid-catalyzed sol-gel polymerizations of alpha,omega-bis(triethoxysilyl)-alkanes substantially lengthen gel times for monomers with ethylene (1), propylene (2), and butylene (3) bridging groups. These cyclization reactions were found, using mass spectrometry and Si-29 NMR spectroscopy, to lead preferentially to monomeric and dimeric products based on six- and seven-membered disilsesquioxane rings. 1,2-Bis(triethoxysilyl)ethane (1) reacts under acidic conditions to give a bicyclic dimer (5) that is composed of two annelated seven-membered rings. Under the same conditions, 1,3-bis(triethoxysilyl)propane (2), 1,4-bis(triethoxysilyl)butane (3), and Z-1,4-bis(triethoxysilyl)but-2-ene (10) undergo an intramolecular condensation reaction to give the six- and seven-membered cyclic disilsesquioxanes 6, 7, and 11. Subsequently, these cyclic monomers slowly react to form the tricyclic dimers 8, 9, and 12. With NaOH as polymerization catalyst, these cyclic silsesquioxanes readily reacted to afford gels that were shown by CP MAS Si-29 NMR and infrared spectroscopies to retain some cyclic structures. Comparison of the porosity and microstructure of xerogels prepared from the cyclic monomers 6 and 7 with those of gels prepared directly from their acyclic precursors 2 and 3 indicates that the final pore structure of the xerogels is markedly dependent on the nature of the precursor. In addition, despite the fact that the monomeric cyclic disilsesquioxane species cannot be isolated from 1-3 under basic conditions due to their rapid rate of gelation, spectroscopic techniques also detected the presence of the cyclic structures in the resulting polymeric gels.

  DOI：

  10.1021/ja982751v
• 作为产物：
  描述：

  三乙氧基硅烷 、 烯丙基三乙氧基硅烷 在 iron(II) tetrafluoroborate hexahydrate 、 2,6-bis[1-((2,6-diethylphenyl)imino)ethyl]pyridine 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 以60%的产率得到1,3-bis(triethoxysilyl)propane
  参考文献：
  名称：

  区域发散的氢化硅烷化，氢化，[2π+2π]-环加成反应和使用抗衡离子活化的土壤富集金属催化的C–H硼化†

  摘要：

  由于产生活性低氧化态催化剂所需的通常具有挑战性的实际要求，富含地球的金属催化的广泛采用落后于第二行和第三行的过渡金属。在这里，我们报告了使用铁和钴的预催化剂跨越五个反应类别的单一内源性活化方案的发展。这种简单的催化歧管使用市售的板凳稳定的四氟硼酸铁或钴盐进行区域发散性的烯烃和炔烃氢化硅烷化，1,3-二烯氢化硅烷化，氢化，[2π+2π]-环加成和CHH硼化。通过氟化物从抗衡离子上解离，原位形成氢化活化剂并生成低氧化态催化剂来进行活化。

  DOI：

  10.1039/c8sc05391j

文献信息

• Regiodivergent hydrosilylation, hydrogenation, [2π + 2π]-cycloaddition and C–H borylation using counterion activated earth-abundant metal catalysis
  作者：Riaz Agahi、Amy J. Challinor、Joanne Dunne、Jamie H. Docherty、Neil B. Carter、Stephen P. Thomas

  DOI：10.1039/c8sc05391j

  日期：——

  The widespread adoption of earth-abundant metal catalysis lags behind that of the second- and third-row transition metals due to the often challenging practical requirements needed to generate the active low oxidation-state catalysts. Here we report the development of a single endogenous activation protocol across five reaction classes using both iron- and cobalt pre-catalysts. This simple catalytic

  由于产生活性低氧化态催化剂所需的通常具有挑战性的实际要求，富含地球的金属催化的广泛采用落后于第二行和第三行的过渡金属。在这里，我们报告了使用铁和钴的预催化剂跨越五个反应类别的单一内源性活化方案的发展。这种简单的催化歧管使用市售的板凳稳定的四氟硼酸铁或钴盐进行区域发散性的烯烃和炔烃氢化硅烷化，1,3-二烯氢化硅烷化，氢化，[2π+2π]-环加成和CHH硼化。通过氟化物从抗衡离子上解离，原位形成氢化活化剂并生成低氧化态催化剂来进行活化。
• Manganese‐Catalyzed Hydrofunctionalization of Alkenes
  作者：Jonathan R. Carney、Barry R. Dillon、Leonie Campbell、Stephen P. Thomas

  DOI：10.1002/anie.201805483

  日期：2018.8.13

  The manganese‐catalyzed hydrosilylation and hydroboration of alkenes has been developed using a single manganese(II) precatalyst and reaction protocol. Both reactions proceed with excellent control of regioselectivity and in high yields across a variety of sterically and electronically differentiated substrates (25 examples). Alkoxide activation, using NaOtBu, was key to precatalyst activation and

  锰催化烯烃的氢化硅烷化和氢硼化反应是使用单一的锰（II）预催化剂和反应方案开发的。两种反应均能很好地控制区域选择性，并能在多种空间和电子分化的底物上获得高收率（25个实例）。使用NaO t Bu进行的醇盐活化是催化剂前活化和反应活性的关键。对于这两种已开发的方法，催化剂的负载量都低至0.5 mol％，从而实现了跨各种官能团和以克为单位的催化作用。
• Intramolecular Condensation Reactions of α,ω-Bis(triethoxysilyl)alkanes. Formation of Cyclic Disilsesquioxanes
  作者：Douglas A. Loy、Joseph P. Carpenter、Sharon A. Myers、Roger A. Assink、James H. Small、John Greaves、Kenneth J. Shea

  DOI：10.1021/ja961409k

  日期：1996.1.1

  alkylene-bridging groups had a pronounced effect on the competition between cyclization and polymerization of alpha},omega}-bis(triethoxysilyl)alkanes and on the formation of polymeric gels. While the intramolecular reaction clearly slows gelation, the cyclic disilsesquioxanes are still tetrafunctional monomers theoretically capable of forming polymeric gels. If the ring structures, which bear a striking resemblence

  在本文中，我们使用质谱和 sup 29}Si NMR 光谱发现亚烷基桥连基团的长度对 alpha},omega}-bis(triethoxysilyl )烷烃和聚合物凝胶的形成。虽然分子内反应明显减缓了凝胶化，但环状二倍半硅氧烷仍然是理论上能够形成聚合物凝胶的四官能单体。如果通过聚合保留与碳水化合物惊人相似的环结构，则所得聚（环状二倍半硅氧烷）凝胶可能与支链或交联碳水化合物（如纤维素或壳聚糖）具有结构相似性。在碱催化的溶胶-凝胶聚合条件下，3 和 4（六元和七元环状二倍半硅氧烷、分别）快速反应以产生具有显着开环的凝胶，这由 sup 29}Si 化学位移在固态 (CP MAS) NMR 光谱中确定。然而，在酸性条件下制备的凝胶表明聚合物中保留了部分或全部环状二倍半硅氧烷官能团。13 参考，1 图。
• Pomerantseva, M. G.; Belyakova, Z. V.; Shchepinov, S. A., Journal of general chemistry of the USSR, 1984, vol. 54, # 2, p. 316 - 318
  作者：Pomerantseva, M. G.、Belyakova, Z. V.、Shchepinov, S. A.、Efimova L. A.、Chernyshev, E. A.

  DOI：——

  日期：——
• Sulfur-Modified SBA-15 Supported Amorphous Palladium with Superior Catalytic Performance for Aerobic Oxidation of Alcohols
  作者：Kun Liu、Zhaoxiang Chen、Zhiqiang Hou、Yuanyuan Wang、Liyi Dai

  DOI：10.1007/s10562-013-1184-2

  日期：2014.5

  A series of sulfur-modified SBA-15 supported amorphous palladium catalysts are prepared, and the effects of preparation parameters on the aerobic oxidation of benzyl alcohol are systematically investigated. The optimal catalyst exhibits remarkably enhanced catalytic activity (conversion 100 % and selectivity 99 %) and could be separated conveniently. The catalysts are characterized by X-ray diffraction patterns, BET, ICP, X-ray photoelectron spectroscopy, CO chemisorption and transmitting electron microscopy, and the results show that disulfur bond framework in the optimal catalyst act as both a stable linker and a good chelator for Pd species. Pd2+ is reduced to Pd-0 with the increasement of the carbon chain lengths between sulfur bonds, which is the cause of deactivation. The mechanism is that a base abstracts a proton from the coordinated alcohol to form a Pd alcoholate species that subsequently undergo beta-hydride elimination to give benzyl aldehyde, which is confirmed by the catalytic and characteristic results.