tetraoctylsilane | 3429-74-1

• 分子结构分类: 有机化合物 - 碳氢化合物衍生物
• 英文名称: tetraoctylsilane
• CAS: 3429-74-1
• 化学式: C₃₂H₆₈Si
• 分子量: 480.977
• InChiKey: CZFVBIJYVFABOJ-UHFFFAOYSA-N

物化性质

• 沸点：
  519.0±18.0 °C(Predicted)
• 密度：
  0.811±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  12.88
• 重原子数：
  33
• 可旋转键数：
  28
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

安全信息

• 海关编码：
  2931900090

反应信息

• 作为反应物：
  描述：

  tetraoctylsilane 、 以 二氯甲烷 为溶剂， 反应 16.0h， 生成 C₂₆H₅₁F₃O₂Si
  参考文献：
  名称：

  使用三（三氟乙酸盐）碘对未活化四烷基硅烷中的 Si-C(sp3) 键进行化学选择性裂解

  摘要：

  有机硅烷是有机化学中合成有用的试剂和前体。然而，未活化的 Si-C(sp3) 键在常规反应条件下的典型惰性阻碍了简单的四烷基硅烷在有机合成中的应用。在此，我们报告了使用三（三氟乙酸）碘对未活化四烷基硅烷的 Si-C(sp3) 键进行化学选择性裂解。该反应在温和条件下（-50°C 至室温）顺利进行，并耐受各种极性官能团，从而使随后的 Tamao-Fleming 氧化能够提供相应的醇。该反应的核磁共振实验和密度泛函理论计算表明，烷基从 Si 转移到 I(III) 中心和 Si-O 键的形成协同进行，得到烷基-λ3-碘烷和三氟乙酸甲硅烷基酯。开发的方法能够使用未活化的四烷基硅烷作为高度稳定的合成前体。

  DOI：

  10.1021/jacs.0c11645
• 作为产物：
  描述：

  正辛基镁溴盐 在 四氯化硅 作用下， 生成 tetraoctylsilane
  参考文献：
  名称：

  Petrow; Tschernyschew, Doklady Akademii Nauk SSSR, 1952, vol. 86, p. 737

  摘要：

  DOI：

文献信息

• SATURATED AND UNSATURATED SILAHYDROCARBONS VIA IRON AND COBALT PYRIDINE DIIMINE CATALYZED OLEFIN SILYLATION
  申请人：Lewis Kenrick Martin

  公开号：US20140330036A1

  公开（公告）日：2014-11-06

  The present invention relates to processes for the synthesis of saturated and unsaturated silahydrocarbons using iron-containing or cobalt-containing catalysts. The processes of the invention can produce tetraalkylsilanes, phenyltrialkylsilanes, substituted phenyltrialkylsilanes and their mixtures, which are useful as lubricants and hydraulic fluids, as well as alkyl alkenylsilanes, phenyl alkenylsilanes and substituted phenyl alkenylsilanes and their mixtures, which are useful in the synthesis of saturated silahydrocarbons and other organofunctional silanes.

  本发明涉及使用含铁或含钴催化剂合成饱和和不饱和硅烃的过程。该发明的过程可以生产四烷基硅烷、苯基三烷基硅烷、取代苯基三烷基硅烷及其混合物，这些对润滑剂和液压油很有用，以及烷基烯基硅烷、苯基烯基硅烷和取代苯基烯基硅烷及其混合物，这些对合成饱和硅烃和其他有机官能硅烷很有用。
• Formal SiH4 chemistry using stable and easy-to-handle surrogates
  作者：Antoine Simonneau、Martin Oestreich

  DOI：10.1038/nchem.2329

  日期：2015.10

  Monosilane (SiH4) is far less well behaved than its carbon analogue methane (CH4). It is a colourless gas that is industrially relevant as a source of elemental silicon, but its pyrophoric and explosive nature makes its handling and use challenging. Consequently, synthetic applications of SiH4 in academic laboratories are extremely rare and methodologies based on SiH4 are underdeveloped. Safe and controlled alternatives to the substituent redistribution approaches of hydrosilanes are desirable and cyclohexa-2,5-dien-1-ylsilanes where the cyclohexa-1,4-diene units serve as placeholders for the hydrogen atoms have been identified as potent surrogates of SiH4. We disclose here that the commercially available Lewis acid tris(pentafluorophenyl)borane, B(C6F5)3, is able to promote the release of the Si–H bond catalytically while subsequently enabling the hydrosilylation of C–C multiple bonds in the same pot. The net reactions are transition-metal-free transfer hydrosilylations with SiH4 as a building block for the preparation of various hydrosilanes. Cyclohexa-2,5-dien-1-yl groups bound to silicon act as masked Si–H bonds that can be released by the action of tris(pentafluorophenyl)borane (B(C6F5)3). In this way, hazardous SiH4 is unleashed from appropriately substituted precursors and engages in alkene hydrosilylation promoted by the same boron catalyst. The overall process is a transfer hydrosilylation of alkenes with monosilane.

  甲硅烷(SiH4)的性质远不如其碳类似物甲烷(CH4)稳定。它是一种无色气体,在工业上作为元素硅的来源具有重要意义,但其易燃易爆的特性使得其处理和使用颇具挑战性。因此,SiH4在学术实验室的合成应用极为罕见,基于SiH4的方法学也尚未充分发展。寻找安全可控的替代方案以取代氢硅烷的取代重分配方法是可取的,而含有环己-2,5-二烯基团的环己-1,4-二烯单元作为氢原子的占位符的硅烷已被确认为SiH4的有效替代品。我们在此揭示,商业上可获得的Lewis酸三(五氟苯基)硼烷,B(C6F5)3,能够催化释放Si–H键,随后在同一反应器中实现C–C多重键的氢硅化反应。净反应是一种无过渡金属参与的转移氢硅化反应,其中SiH4作为制备各种氢硅烷的构建单元。与硅原子结合的环己-2,5-二烯基团作为掩蔽的Si–H键,可以通过三(五氟苯基)硼烷(B(C6F5)3)的作用释放出来。通过这种方式,危险物质SiH4从适当取代的前体中释放出来,并在同一硼催化剂的促进下参与烯烃的氢硅化反应。整个过程是一种烯烃的单硅烷转移氢硅化反应。
• Preparation of Tetraalkylsilanes from Trichloromethylsilane and Trioctylaluminum
  作者：Edward T. Sabourin、Anatoli Onopchenko

  DOI：10.1246/bcsj.62.3691

  日期：1989.11

  The synthesis of methyltrioctylsilane has been achieved in a single-step from commercially available trichloromethylsilane and trioctylaluminum. Co-products resulting from alkyl group redistribution are minimized by addition of sodium or lithium halides. Use of potassium or rubidium halides drastically changes the course of the reaction to produce methyldioctylsilane as the major product.

  利用市售的三氯甲基硅烷和三辛基铝，一步即可合成甲基三辛基硅烷。通过加入钠或锂卤化物，可将烷基重新分布产生的副产物降至最低。使用钾或铷卤化物会大大改变反应的过程，从而生成主要产品甲基二辛基硅烷。
• Production of saturated and unsaturated silahydrocarbon mixtures using
  申请人：Gulf Research & Development Company

  公开号：US04572791A1

  公开（公告）日：1986-02-25

  The silahydrocarbon product containing at least 75 weight percent of saturated silahydrocarbons with the remainder being unsaturated silahydrocarbons is produced by a process in which admixture comprising (A) at least one alpha-olefin containing from 2 to about 20 carbon atoms per molecule, and (B) at least one alkylsilane selected from the group consisting of (i) a dialkylsilane having the formula R--SiH.sub.2 --R.sub.1 (ii) a trialkylsilane having the formula ##STR1## and (iii) mixtures thereof, wherein R and R.sub.1, the same or different, each represent an alkyl radical of from one to 20 carbon atoms per molecule with a catalyst comprising a homogeneous rhodium-containing catalyst or a heterogeneous rhodium-containing catalyst in a halogen-free inert solvent, under hydrosilylation reaction conditions to produce a mixture containing saturated and unsaturated silane hydrocarbons useful as lubricants. The unsaturated silane hydrocarbons can be substituted with sulfur to provide improved lubricating characteristics.

  含有至少75重量％饱和硅氢化合物的硅氢化合物产品是通过以下过程生产的：将混合物（A）至少包含每个分子中2到约20个碳原子的α-烯烃，和（B）至少包含以下组中选择的一种烷基硅烷混合：（i）具有R-SiH.sub.2-R.sub.1公式的二烷基硅烷，（ii）具有以下公式的三烷基硅烷##STR1##和（iii）其混合物，其中R和R.sub.1，相同或不同，分别表示每个分子中的一种含有1到20个碳原子的烷基基团，与含有均相或非均相含铑催化剂的卤素无溶剂，在氢硅烷化反应条件下产生含有饱和和不饱和硅氢烃的混合物，可用作润滑剂。不饱和硅氢烃可用硫代替，以提供改良的润滑特性。
• Silahydrocarbons from alkylchlorosilanes
  申请人：Gulf Research & Development Company

  公开号：US04595777A1

  公开（公告）日：1986-06-17

  A process for the production of tetra- and trialkylsilanes which comprises reacting (A) an alkylchlorosilane having the formula R.sub.x SiCl.sub.(4-x) wherein R is an alkyl radical containing from one to three carbon atoms per molecule and x is an integer from 0 to 3, with (B) a trialkylaluminum compound having the formula ##STR1## wherein R.sub.1, R.sub.2 and R.sub.3 are the same or different and represent alkyl radicals containing from 6 to 20 carbon atoms per molecule, in a reaction zone, said reaction being conducted under hydrosilylation conditions. Selectivity to tetra- or trialkylsilanes, respectively, is controlled by the addition of particular alkaline metal salts to the reaction zone.

  一种生产四烷基和三烷基硅烷的方法，包括将（A）化学式为R.sub.x SiCl.sub.(4-x)的烷基氯硅烷与（B）化学式为##STR1##的三烷基铝化合物在反应区反应，其中R是每个分子含有1至3个碳原子的烷基基团，x是0至3的整数。该反应在加氢硅化条件下进行。通过向反应区添加特定的碱金属盐来控制四烷基或三烷基硅烷的选择性。