1,4-bis(triethoxysilyl)butane | 52885-14-0

• 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: 1,4-bis(triethoxysilyl)butane
• 英文别名: 3,10-Dioxa-4,9-disiladodecane, 4,4,9,9-tetraethoxy-；triethoxy(4-triethoxysilylbutyl)silane
• CAS: 52885-14-0
• 化学式: C₁₆H₃₈O₆Si₂
• 分子量: 382.645
• InChiKey: PQVPWZHUJMEZSA-UHFFFAOYSA-N

物化性质

• 沸点：
  250 °C(Press: 750 Torr)
• 密度：
  0.951±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.86
• 重原子数：
  24
• 可旋转键数：
  17
• 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：

  1,4-bis(triethoxysilyl)butane 在 盐酸 、 chromium(III) acetylacetonate 作用下， 以 乙醇 为溶剂， 反应 1.5h， 以68%的产率得到2,2,7,7-tetraethoxy-2,7-disilaoxacycloheptane
  参考文献：
  名称：

  α,ω-双（三乙氧基甲硅烷基）烷烃的分子内缩合反应。环状二倍半硅氧烷的形成

  摘要：

  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。

  DOI：

  10.1021/ja961409k
• 作为产物：
  描述：

  三乙氧基硅烷 、 3-丁烯三乙氧基硅烷 在 dihydrogen hexachloroplatinate 作用下， 以 苯 为溶剂， 反应 20.0h， 以48%的产率得到1,4-bis(triethoxysilyl)butane
  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

文献信息

• 一种有机硅偶联剂及其制备方法
  申请人：北京航空航天大学

  公开号：CN110229182A

  公开（公告）日：2019-09-13

  本发明提供了一种有机硅偶联剂及其制备方法，该方法在高选择性硅氢加成催化剂的催化下，含硅烷基团的分子和含烯烃基团的分子进行硅氢加成反应，生成有机硅偶联剂。所述高选择性硅氢加成催化剂利用烯烃与铂原子形成弱的配位键更有利于铂原子的活化，同时有机笼状配体避免了铂原子的团聚，配合物催化剂所形成的空间立体结构能够产生非常大的空间位阻，极大的提高了硅氢加成产物的选择性。本发明的制备方法能够制备Karstedt’s催化剂不能催化的硅氢加成反应来制备得到新型的偶联剂。
• Competitive dehydrogenative silylation and hydrogenative dimerization of vinyltriethoxysilane catalyzed by the [Ni(acac)2] + PPh3 system, intermediate and mechanistic implications
  作者：B. Marciniec、H. Maciejewski、J. Guliński、B. Maciejewska、W. Duczmal

  DOI：10.1016/0022-328x(96)06355-3

  日期：1996.8

  [Ni(acac)C2H5(PPh3)](C) has been shown to be an essential intermediate in the reaction between HSi(OC2H5)3 and vinyltrisubstituted silanes catalyzed by the system [Ni(acac)2] + PPh3 at room temperature, but only after oxygenation of the coordinated triphenylphosphive. The stoichiometric and catalytic reactions of complex C with the substrates lead to catalysed, competitive dehydrogenative silylation

  已显示[Ni（acac）C 2 H 5（PPh 3）]（C）是HSi（OC 2 H 5）3与系统[Ni（acac）2催化的乙烯基三取代硅烷之间的反应中必不可少的中间体] + PPh 3在室温下进行，但仅在配位的三苯基膦酸酯氧化后才能进行。配合物C与底物的化学计量和催化反应导致乙烯基硅烷发生催化的竞争性脱氢甲硅烷基化和氢化二聚反应，这些反应发生在乙烯基硅烷插入Ni-H，NiSi和NiC键之后。
• Catalysis of hydrosilylation Part XXV. Effect of nickel(O) and nickel(II) complex catalysts on dehydrogenative silylation, hydrosilylation and dimerization of vinyltriethoxysilane
  作者：Bogdan Marciniec、Hieronim Maciejewski、Uwe Rosenthal

  DOI：10.1016/0022-328x(94)87198-1

  日期：1994.12

  of vinylsilane, side reactions can be practically eliminated. Tertiary phosphine and phosphite ligands of nickel acetylacetonate (Ni(acac) 2 · 2PR3) stop the consecutive reactions of bis(silyl)ethene but in the presence of σ-basic and bulky tricyclohexylphosphine the system catalyses selectively the regular hydrosilylation of bis(silyl)ethene.

  Ni（O）和Ni（II）膦和非膦配合物对乙烯基三乙氧基硅烷与三乙氧基硅烷的竞争性连续反应的一般催化作用已被观察到，主要产生脱氢甲硅烷基化和氢化二聚化的产物，以及规则的氢硅烷化，歧化的产物。底物和产物的副反应-双（甲硅烷基）乙烯。在过量的乙烯基硅烷中，实际上可以消除副反应。乙酰丙酮化镍（Ni（acac）2 ·2PR 3）的叔膦和亚磷酸酯配体终止了双（甲硅烷基）乙烯的连续反应，但在存在σ-碱性和庞大的三环己基膦的情况下，该系统选择性催化双（甲硅烷基）的定期硅氢加成反应乙烯。
• Catalysis of hydrosilylation
  作者：H. Maciejewski、B. Marciniec、I. Kownacki

  DOI：10.1016/s0022-328x(99)00685-3

  日期：2000.3

  The nickel equivalent of Karstedt catalyst [Ni(eta-CH2=CHSiMe2)(2)O}(2)mu-(eta-CH2=CHSiMe2}(2)O}] (1) appeared to be a very efficient catalyst for dehydrogenative coupling of vinyl derivatives (styrene, vinylsilanes, vinylsiloxanes) with trisubstituted silanes HSi(OEt)(3), HSiMe2Ph. The reaction occurs via three pathways of dehydrogenative coupling, involving formation of an unsaturated compound as the main product as well as a hydrogenated olefin (DS-1) pathway, hydrogenated dimeric olefin (DS-2) and dihydrogen (DC), respectively. The reaction is accompanied by side hydrosilylation. Stoichiometric reactions of 1 with styrene and triethoxysilane, in particular synthesis of the bis(triethoxysilyl) (divinyltetramethyldisiloxane) nickel complex 3 and the first documented insertion of olefin (styrene) into Ni-Si bond of complex 3, as well as all catalytic data have allowed us to propose a scheme of catalysis of this complex reaction by 1. (C) 2000 Elsevier Science S.A. All rights reserved.
• Cyclization Phenomena in the Sol−Gel Polymerization of α,ω-Bis(triethoxysilyl)alkanes and Incorporation of the Cyclic Structures into Network Silsesquioxane Polymers
  作者：Douglas A. Loy、Joseph P. Carpenter、Todd M. Alam、Raef Shaltout、Peter K. Dorhout、John Greaves、James H. Small、Kenneth J. Shea

  DOI：10.1021/ja982751v

  日期：1999.6.1

  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.