triethyl(4-methylbenzyl)silane | 18415-20-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: triethyl(4-methylbenzyl)silane
• 英文别名: Triethyl[(4-methylphenyl)methyl]silane；triethyl-[(4-methylphenyl)methyl]silane
• CAS: 18415-20-8
• 化学式: C₁₄H₂₄Si
• 分子量: 220.43
• InChiKey: OLMUQTQOTLUNCC-UHFFFAOYSA-N

物化性质

• 沸点：
  102 °C(Press: 2 Torr)
• 密度：
  0.8968 g/cm3

计算性质

• 辛醇/水分配系数(LogP)：
  4.59
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  triethyl(4-methylbenzyl)silane 、 溶剂黄146 在 K5 作用下， 以 水 为溶剂， 生成 (4-甲基苯基)甲醇 、 乙酸对甲基苄酯
  参考文献：
  名称：

  A kinetic study of the electron-transfer-initiated carbon-silicon bond cleavage reactions of benzyltrialkylsilanes promoted by dodecatungstocobalt(III)ate ion

  摘要：

  The reactions of some ring-substituted benzyltrimethylsilanes (1Z), (p-methylbenzyl)triethylsilane (2), (p-methylbenzyl)triisopropylsilane (3), and (p-methoxybenzyl)triisopropylsilane (4) with potassium 12-tungstocobalt(III)ate, K5[CoIIIW12O40] (CO(III)W), have been studied in AcOH-H2O. In all cases desilylated products, benzyl acetates, and benzyl alcohols have been obtained, with a 2:1 oxidant to substrate stoichiometry. A kinetic investigation has shown that the reactions of 1Z and 2 are strictly first order in Co(III)W and first order in the substrate. Added salts (NaClO4, NaOAc) decrease the rate, whereas no retarding effect by Co(II)W has been noted. In contrast, the reaction of 4 is no longer first order in Co(III)W and the rate is significantly decreased by added Co(II)W. These data have been interpreted in terms of an electron-transfer mechanism, in which a benzyltrialkylsilane radical cation is formed and then undergoes a C-Si bond cleavage to form a benzyl radical. Reaction of this radical with Co(III)W leads to the products. In the reactions of 1Z and 2 the rate-determining step is the transfer of the electron from the substrate to Co(III)W, whereas in the reaction of 4 the slow step is the one where the C-Si bond cleavage takes place. The mechanistic changeover is probably related to the much lower rate of C-Si bond cleavage in 4+. than in 1Z+. and 2+., due to the fact that in the former cation radical nucleophilic attack at silicon is made difficult by the bulky isopropyl groups. The kinetic data for the reactions of 1Z and 2 fit the Marcus equation for a reorganization energy lambda of 43 +/- 1 kcal mol-1. From this value a lambda-value of 61 kcal mol-1 for the couple ArCH2SiMe3+./ArCH2SiMe3 has been evaluated, which is somewhat higher than that found for a number of ArCH3+./ArCH3 Systems. The possible reasons for this difference are discussed on the basis of ab initio calculations (STO-3G) concerning bond distances and angles in PhCH3+. and PhCH2SiH3+..

  DOI：

  10.1021/jo00043a028
• 作为产物：
  描述：

  三乙基硅烷 、 对二甲苯 在 6Zr⁽⁴⁺⁾*6C₂₀H₁₂O₄^(2-)*8O^(2-)*4Cl^(1-)*4Co⁽²⁺⁾ 、 三乙基硼氢化钠 作用下， 以 neat (no solvent) 为溶剂， 反应 48.0h， 生成 triethyl(4-methylbenzyl)silane
  参考文献：
  名称：

  STABILIZATION OF ACTIVE METAL CATALYSTS AT METAL-ORGANIC FRAMEWORK NODES FOR HIGHLY EFFICIENT ORGANIC TRANSFORMATIONS

  摘要：

  基于后合成金属化的次级构建单元（SBU）端部或桥接的OH或OH2基团与金属前体或其他后合成操作的金属有机框架（MOFs）组成物被描述。这些MOFs提供了一系列多功能的可回收和可重复使用的单位固体催化剂，用于催化各种不对称有机转化，包括对苯基C—H键的区域选择性硼化和硅基化，烯烃、亚胺、醛酮、硝基芳烃和杂环化合物的加氢，氢硼化，氢磷化和环化反应。这些固体催化剂也可以集成到流动反应器或超临界流体反应器中。

  公开号：

  US20180361370A1

文献信息

• Iron Porphyrin Catalyzed Insertion Reaction of <i>N</i>-Tosylhydrazone-Derived Carbenes into X–H (X = Si, Sn, Ge) Bonds
  作者：En-Hui Wang、Yuan-Ji Ping、Zong-Rui Li、Hongling Qin、Zhen-Jiang Xu、Chi-Ming Che

  DOI：10.1021/acs.orglett.8b01931

  日期：2018.8.3

  An efficient Fe(TPP)Cl catalyzed insertion reaction of in situ generated benzylic carbenes from N-tosylhydrazones into X–H (X = Si, Sn, Ge) was developed. Silanes bearing tertiary, secondary, and primary (3°, 2°, and 1°) Si–H bonds all reacted well to afford insertion products in moderate to high yields (up to 97%), and the reaction time could be significantly shortened to 1 h under microwave irradiation

  开发了一种有效的Fe（TPP）Cl催化的原位生成的苄基卡宾从N-甲苯磺酰into插入X–H（X = Si，Sn，Ge）的插入反应。带有叔，仲和伯（3°，2°和1°）Si-H键的硅烷都能很好地反应，从而以中等至高产率（高达97％）提供插入产物，并且反应时间可以大大缩短在微波照射下至1小时。开发了一种可编程的逐步双插入策略，用于合成不对称的四取代的硅烷。
• One-Pot Rapid Access to Benzyl Silanes, Germanes, and Stannanes from Toluenes Mediated by a LiN(SiMe₃)₂/CsCl System
  作者：Yaqi Yuan、Yuanyun Gu、Yan-En Wang、Jiali Zheng、Jiaying Ji、Dan Xiong、Fei Xue、Jianyou Mao

  DOI：10.1021/acs.joc.2c01612

  日期：2022.11.4

  Organo-silanes, germanes, and stannanes are considered to be conducive to the development of cross-coupling reactions because they are stable, nontoxic, and easy to handle. Using feedstock toluenes, one-pot direct benzylic C–H silylations, germylations, and stannylations are developed. Simply combining toluenes, LiN(SiMe3)2/CsCl, and R3MCl (M = Si, Ge, Sn) generates a diverse array of bench-stable

  有机硅烷、锗烷和锡烷被认为有利于交叉偶联反应的发展，因为它们稳定、无毒且易于处理。使用原料甲苯，开发了一锅直接苄基 C-H 甲硅烷基化、胚芽化和单烷基化。简单地将甲苯、LiN(SiMe 3 ) 2 /CsCl 和 R 3 MCl (M = Si、Ge、Sn) 组合起来，就可以生成各种台式稳定的苄基硅烷、锗烷和锡烷（38 个例子，53-90% 的产率）。这里开发的合成很容易大规模访问。
• Deoxygenative Silylation of C(sp³)–O Bonds with Hydrosilane by Cooperative Catalysis of Gold Nanoparticles and Solid Acids
  作者：Hiroki Miura、Yuki Yasui、Yosuke Masaki、Masafumi Doi、Tetsuya Shishido

  DOI：10.1021/acscatal.3c00973

  日期：2023.5.19

  Efficient deoxygenative silylation of C(sp3)–O bonds with hydrosilanes by supported Au catalysts is described. Gold nanoparticles supported on TiO2 enabled various hydrosilanes to be used as sources of silyl groups in C–Si cross-coupling reactions. A variety of alkyl acetates and propargyl carbonates participated in the Au-catalyzed reactions to furnish the corresponding alkyl and allenylsilanes in

  描述了负载型 Au 催化剂对 C(sp 3 )–O 键与氢硅烷的有效脱氧硅烷化。负载在 TiO 2上的金纳米粒子使各种氢硅烷能够在 C-Si 交叉偶联反应中用作甲硅烷基的来源。各种乙酸烷基酯和碳酸炔丙酯参与了金催化的反应，以高产率提供相应的烷基和烯丙基硅烷。此外，Au/TiO 2对环醚的开环甲硅烷基化也有效。详细的机理研究证实标题反应涉及甲硅烷基和烷基自由基中间体的形成，而 Au 纳米颗粒作为单电子转移催化剂与金属氧化物表面的路易斯酸位点的合作是氢硅烷异常反应性的原因特定的 C(sp 3 )–Si 键形成。
• STABILIZATION OF ACTIVE METAL CATALYSTS AT METAL-ORGANIC FRAMEWORK NODES FOR HIGHLY EFFICIENT ORGANIC TRANSFORMATIONS
  申请人：The University of Chicago

  公开号：US20180361370A1

  公开（公告）日：2018-12-20

  Metal-organic framework (MOFs) compositions based on post¬synthetic metalation of secondary building unit (SBU) terminal or bridging OH or OH 2 groups with metal precursors or other post-synthetic manipulations are described. The MOFs provide a versatile family of recyclable and reusable single-site solid catalysts for catalyzing a variety of asymmetric organic transformations, including the regioselective boryiation and siiylation of benzyiic C—H bonds, the hydrogenation of aikenes, imines, carbonyls, nitroarenes, and heterocycles, hydroboration, hydrophosphination, and cyclization reactions. The solid catalysts can also be integrated into a flow reactor or a supercritical fluid reactor.

  基于后合成金属化的次级构建单元（SBU）端部或桥接的OH或OH2基团与金属前体或其他后合成操作的金属有机框架（MOFs）组成物被描述。这些MOFs提供了一系列多功能的可回收和可重复使用的单位固体催化剂，用于催化各种不对称有机转化，包括对苯基C—H键的区域选择性硼化和硅基化，烯烃、亚胺、醛酮、硝基芳烃和杂环化合物的加氢，氢硼化，氢磷化和环化反应。这些固体催化剂也可以集成到流动反应器或超临界流体反应器中。
• A kinetic study of the electron-transfer-initiated carbon-silicon bond cleavage reactions of benzyltrialkylsilanes promoted by dodecatungstocobalt(III)ate ion
  作者：Enrico Baciocchi、Manuela Crescenzi、Elisabetta Fasella、Mario Mattioli

  DOI：10.1021/jo00043a028

  日期：1992.8

  The reactions of some ring-substituted benzyltrimethylsilanes (1Z), (p-methylbenzyl)triethylsilane (2), (p-methylbenzyl)triisopropylsilane (3), and (p-methoxybenzyl)triisopropylsilane (4) with potassium 12-tungstocobalt(III)ate, K5[CoIIIW12O40] (CO(III)W), have been studied in AcOH-H2O. In all cases desilylated products, benzyl acetates, and benzyl alcohols have been obtained, with a 2:1 oxidant to substrate stoichiometry. A kinetic investigation has shown that the reactions of 1Z and 2 are strictly first order in Co(III)W and first order in the substrate. Added salts (NaClO4, NaOAc) decrease the rate, whereas no retarding effect by Co(II)W has been noted. In contrast, the reaction of 4 is no longer first order in Co(III)W and the rate is significantly decreased by added Co(II)W. These data have been interpreted in terms of an electron-transfer mechanism, in which a benzyltrialkylsilane radical cation is formed and then undergoes a C-Si bond cleavage to form a benzyl radical. Reaction of this radical with Co(III)W leads to the products. In the reactions of 1Z and 2 the rate-determining step is the transfer of the electron from the substrate to Co(III)W, whereas in the reaction of 4 the slow step is the one where the C-Si bond cleavage takes place. The mechanistic changeover is probably related to the much lower rate of C-Si bond cleavage in 4+. than in 1Z+. and 2+., due to the fact that in the former cation radical nucleophilic attack at silicon is made difficult by the bulky isopropyl groups. The kinetic data for the reactions of 1Z and 2 fit the Marcus equation for a reorganization energy lambda of 43 +/- 1 kcal mol-1. From this value a lambda-value of 61 kcal mol-1 for the couple ArCH2SiMe3+./ArCH2SiMe3 has been evaluated, which is somewhat higher than that found for a number of ArCH3+./ArCH3 Systems. The possible reasons for this difference are discussed on the basis of ab initio calculations (STO-3G) concerning bond distances and angles in PhCH3+. and PhCH2SiH3+..