(dichloromethyl)methylbis(trimethylsilyl)silane | 15816-05-4

• 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: (dichloromethyl)methylbis(trimethylsilyl)silane
• 英文别名: 2-(Dichloromethyl)-1,1,1,2,3,3,3-heptamethyltrisilane；dichloromethyl-methyl-bis(trimethylsilyl)silane
• CAS: 15816-05-4
• 化学式: C₈H₂₂Cl₂Si₃
• 分子量: 273.425
• InChiKey: KOXQKZYYFQCRRL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.24
• 重原子数：
  13
• 可旋转键数：
  3
• 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

反应信息

• 作为反应物：
  描述：

  (dichloromethyl)methylbis(trimethylsilyl)silane 、 2,4,6-triisopropylphenyl lithium 以 乙醚 为溶剂， 反应 12.0h， 以44%的产率得到methylbis(2,4,6-triisopropylphenyl)[bis(trimethylsilyl)methyl]silane
  参考文献：
  名称：

  (二氯甲基)低聚硅烷 R(Me3Si)2Si-CHCl2 (R = Me, Ph, Me3Si) 与有机锂试剂的反应和新型动力学稳定的 Silenes 的合成

  摘要：

  二氯甲基低聚硅烷 R1(Me3Si)2Si-CHCl2 (1a,b) (1a: R1 = Me; 1b: R1 = Ph)，分别用氯仿和叔叔钾处理甲基双（三甲基甲硅烷基）硅烷或苯基双（三甲基甲硅烷基）硅烷制备-丁醇盐，用有机锂试剂 R2Li (R2 = Me, Ph) 处理，生成中间体有机锂衍生物 R1R22Si-CLi(SiMe3)2 (10)。在水性后处理期间水解 10 得到 [双（三甲基甲硅烷基）甲基] 硅烷 R1R22Si-CH(SiMe3)2 (2)；用氯三甲基硅烷淬灭反应混合物得到[三(三甲基甲硅烷基)甲基]硅烷 R1R22Si-C(SiMe3)3 (11)。讨论 10 的形成是通过一系列显着的异构化过程进行的，这些过程涉及瞬态 silene R1R2Si=C(SiMe3)2 (7)，在有效过量的 R2Li 存在下，它立即被捕获，得到 10。通过使用空间拥挤的有机锂衍生物，可以防止

  DOI：

  10.1002/1099-0682(200102)2001:2<481::aid-ejic481>3.0.co;2-6
• 作为产物：
  描述：

  二氯甲烷 、 2-chloroheptamethyltrisilane 生成 (dichloromethyl)methylbis(trimethylsilyl)silane
  参考文献：
  名称：

  Synthesis and properties of 1-and 2-(dichloromethyl)heptamethyltrisilane and related compounds

  摘要：

  DOI：

  10.1021/jo01268a047

文献信息

• The Synthesis of Stable Intramolecularly Dialkylamino‐Coordinated Silenes and Their Methyl Iodide Induced Isomerization into Cyclic Aminosilanes
  作者：Martin Mickoleit、Kathleen Schmohl、Manfred Michalik、Hartmut Oehme

  DOI：10.1002/ejic.200300626

  日期：2004.4

  distances for 1d, 2 and 3 help establish the ylide-like nature of the silenes prepared. Treatment of 1a−d with water produced the silanols 9a−d. Treatment of 1a,b, and d with methyl iodide caused a rearrangement of the silenes, one methyl substituent formally migrating from the coordinated dimethylamino group to the silene carbon atom producing the respective cyclic aminosilanes 11a,b, and d. As the outcome

  （二氯甲基）低聚硅烷 R(Me3Si)2SiCHCl24a-d（4a：R = Me；4b：R = tBu；4c：R = Ph；4d：R = SiMe3）与 8-（二甲氨基）-1-萘基锂的反应导致分子内供体稳定的 silene 1a-d。虽然 1a、b 和 d 被分离为热稳定的黄色结晶化合物，但 1c 无法以纯形式分离，但可以通过 NMR 光谱和质谱以及其与各种底物的化学反应性进行表征。1a 和 1d 的动态 1H NMR 光谱研究揭示了两个 CSiMe3 基团信号的合并。与理论计算一致，这种效应被解释为围绕 silene 双键的内部旋转的结果。这些发现和已知的相对较长的 Si=C 距离为 1d，图 2 和图 3 有助于确定所制备的 silene 的类叶立德性质。用水处理 1a-d 产生了硅烷醇 9a-d。用碘甲烷处理 1a、b 和 d 引起了硅酮的重排，一个甲基取代基形式上从配位的二甲氨基
• Intramolecularly donor-stabilized silenes: Part 6. The synthesis of 1-[2,6-bis(dimethylaminomethyl)phenyl]silenes and their reaction with aromatic aldehydes
  作者：Ute Bäumer、Helmut Reinke、Hartmut Oehme

  DOI：10.1016/j.jorganchem.2005.02.049

  日期：2006.1

  The intramolecularly donor-stabilized silenes (ArRSi)-Si-1=C(SiMe3)(2) (3a-d) (3a: R-1 = Me; 3b: R-1 = t-Bu; 3c: R-1 = Ph; 3d: R-1 = SiMe3; Ar = 2,6-(Me2NCH2)(2)C6H3) were prepared by treatment of the (dichloromethyl)oligosilanes (Me3Si)(2)R-1 Si-CHCl2 (la-l), with 2,6-bis(dimethylaminomethyl)phenyllithium (molar ratio 1:2). For 3c and 3d, X-ray structural analyses were performed indicating that only one dimethylamino group of the tridentate ligand is coordinated to the electrophilic silene silicon atoms, i.e., the central silicon atoms are tetracoordinated. The N -> Si donation leads to pyramidalization at the silene silicon atoms; the configuration at the silene carbon atoms is planar. For a chemical characterization 3a and 3c were treated with water to give the silanols (ArRSi)-Si-1(OH)-CH(SiMe3)(2) (5a,c). Studies of the reactions of 3a and 3c with benzaldehyde, 4-chlorobenzaldehyde or 4-methoxybenzaldehyde, respectively, revealed an unexpected reaction path leading to the substituted 2-oxa-1-sila-1,2,3,4-tetrahydronaphthalenes 12a, 12c, 13 and 14. Both 12a and 12c were structurally characterized by X-ray analyses. The formation of these six-membered cyclic compounds, which is discussed in detail, gives support to a dipolar mechanism for the general reaction of silenes with carbonyl derivatives. (c) 2005 Elsevier B.V. All rights reserved.
• Synthesis and properties of 1-and 2-(dichloromethyl)heptamethyltrisilane and related compounds
  作者：Hideki Sakurai、Hisayoshi Yamamori、Makoto Kumada

  DOI：10.1021/jo01268a047

  日期：1968.4
• Reaction of the (Dichloromethyl)oligosilanes R(Me3Si)2Si−CHCl2 (R = Me, Ph, Me3Si) with Organolithium Reagents and the Synthesis of Novel Kinetically Stabilized Silenes
  作者：Kathleen Schmohl、Helmut Reinke、Hartmut Oehme

  DOI：10.1002/1099-0682(200102)2001:2<481::aid-ejic481>3.0.co;2-6

  日期：2001.2

  silanols, by the addition of methanol to give methoxysilanes and by formal [2+2] cycloadditions with benzaldehyde to afford stable 1,2-oxasiletanes. 1-Methyl-1-(2,4,6-triisopropylphenyl)-2,2-bis(trimethylsilyl)silene (8a), produced as intermediate from 1a and 2,4,6-triisopropylphenyllithium (1:2), proved to be unstable in the presence of excess aryllithium compound. Thus, only the addition product Me(2

  二氯甲基低聚硅烷 R1(Me3Si)2Si-CHCl2 (1a,b) (1a: R1 = Me; 1b: R1 = Ph)，分别用氯仿和叔叔钾处理甲基双（三甲基甲硅烷基）硅烷或苯基双（三甲基甲硅烷基）硅烷制备-丁醇盐，用有机锂试剂 R2Li (R2 = Me, Ph) 处理，生成中间体有机锂衍生物 R1R22Si-CLi(SiMe3)2 (10)。在水性后处理期间水解 10 得到 [双（三甲基甲硅烷基）甲基] 硅烷 R1R22Si-CH(SiMe3)2 (2)；用氯三甲基硅烷淬灭反应混合物得到[三(三甲基甲硅烷基)甲基]硅烷 R1R22Si-C(SiMe3)3 (11)。讨论 10 的形成是通过一系列显着的异构化过程进行的，这些过程涉及瞬态 silene R1R2Si=C(SiMe3)2 (7)，在有效过量的 R2Li 存在下，它立即被捕获，得到 10。通过使用空间拥挤的有机锂衍生物，可以防止