chloro(2-methoxyphenyl)dimethylsilane | 60458-00-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: chloro(2-methoxyphenyl)dimethylsilane
• 英文别名: ClMe2SiC6H4-o-OMe；o-Anisyldimethylchlorosilane；chloro-(2-methoxyphenyl)-dimethylsilane
• CAS: 60458-00-6
• 化学式: C₉H₁₃ClOSi
• 分子量: 200.74
• InChiKey: JDNBWIZGOUSEQO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.35
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  chloro(2-methoxyphenyl)dimethylsilane 在 正丁基锂 、 ammonium cerium(IV) nitrate 、 碳酸氢钠 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 1.5h， 生成 6-Bromo-1-[(2-methoxy-phenyl)-dimethyl-silanyl]-hexan-1-one
  参考文献：
  名称：

  The Scope and Limitations of Intramolecular Radical Cyclizations of Acylsilanes with Alkyl, Aryl, and Vinyl Radicals

  摘要：

  5-Exo cyclizations of primary and secondary radicals with acylsilanes successfully give cyclopentyl silyl ethers. The corresponding 6-exo cyclizations are sensitive to changes of the size of silyl groups. Secondary radicals undergo 6-exo cyclizations with acylsilanes more slowly. Reaction of aryl radical with acylsilane proceeds well for 5-exo cyclization but not for 6-exo cyclization. Vinyl radicals give best results in 5-exo cyclizations with acylsilanes but give low yields (similar to 30%) in 6-exo cyclizations. Intramolecular cyclizations of vinyl radicals with acylsilanes give enol silyl ethers regiospecifically.

  DOI：

  10.1021/jo9711302
• 作为产物：
  描述：

  2-Methoxyphenylmagnesium bromide 在 四氯化碳 、 偶氮二异丁腈 作用下， 以 乙醚 为溶剂， 反应 2.0h， 生成 chloro(2-methoxyphenyl)dimethylsilane
  参考文献：
  名称：

  Oba, Makoto; Kawahara, Yoko; Yamada, Ryo, Journal of the Chemical Society. Perkin Transactions 2 (2001), 1996, vol. 9, p. 1843 - 1848

  摘要：

  DOI：

文献信息

• Alkali Metal Cation π-Interactions in Metalated and Nonmetalated Acetylenes:  π-Bonded Lithiums in the X-ray Crystal Structures of [Li−C⋮C−SiMe₂−C₆H₄−OMe]₆ and [Li−O−CMe₂−C⋮C−H]₆ and Computational Studies
  作者：Bernd Goldfuss、Paul von Ragué Schleyer、Frank Hampel

  DOI：10.1021/ja9622517

  日期：1997.2.1

  205(11) A). This Li−Cα distance differentiation is unique in organolithium hexamers, and is due to Li(C⋮C−R) “side-on-π” and “end-on-σ” contacts, as is shown computationally in H−C⋮C−Li(LiH)2 (20). A second X-ray crystal structure, [Li−O−CMe2−C⋮C−H]6 (22)6, reveals electrostatic π-interactions between the lithiums in the (LiO)6 core and the nonmetalated acetylene groups (Li1−C2 = 2.443(5) A, Li1−C3 = 2.749(6)

  [Li-C⋮C-SiMe2-C6H4-OMe]6 (14)6 的 X 射线晶体结构具有锂离子和乙炔阴离子之间几乎对称的 π 相互作用（Li1-Cβ = 2.353(9) A， Li1−Cα = 2.292(9) A)。这些 π 接触由螯合的邻茴香基甲氧基（Li1-Cα-Cβ = 77.6(4)°，Li1-O1 = 2.169(9) A）促进。(14)6 的 (LiCα)6 核中的 Li-Cα 距离显着不同（Li1α-Cα = 2.132(9) A，Li1b-Cα = 2.205(11) A）。这种 Li-Cα 距离差异在有机锂六聚体中是独一无二的，并且是由于 Li(C⋮C-R) “side-on-π”和“end-on-σ”接触，如 H-C⋮ 中的计算所示C-Li(LiH)2 (20)。第二种 X 射线晶体结构 [Li-O-CMe2-C⋮C-H]6 (22)6，揭示了 (LiO)6 核中的锂与非金属化乙炔基团
• Silylative decarbonylation: a new route to arylsilanes
  作者：Jonathan D. Rich

  DOI：10.1021/ja00197a058

  日期：1989.7

  procedure is tolerant of a variety of aromatic substituents, for example, alkyl, halo, nitro, cyano, imide, acid anhydride, etc., and the synthesis of several new substituted aromatic chlorosilanes containing benzoyl chloride and phthalic anhydride moieties is described. Chloromethyldisilane starting reagents are available from the direct reaction of methyl chloride and silicon, making this methodology

  描述了一种通过钯催化的甲基氯乙硅烷和芳族酰氯反应制备芳族氯硅烷的新合成方法。甲硅烷基化脱羰过程是无溶剂的，可以利用低金属催化剂负载量（500-1,000 ppm Pd），在温和条件（145°C）下进行，并且选择性地以良好的产率（通常为 60-85%）得到芳族氯硅烷。该程序可以容忍多种芳族取代基，例如烷基、卤素、硝基、氰基、酰亚胺、酸酐等，并且描述了几种新的含有苯甲酰氯和邻苯二甲酸酐部分的取代芳族氯硅烷的合成。氯甲基乙硅烷起始试剂可得自氯甲烷与硅的直接反应，
• The influence of functional groups on the ethylene polymerization performance of silsesquioxane-supported Phillips-type catalysts
  作者：Ryuki Baba、Ashutosh Thakur、Patchanee Chammingkwan、Minoru Terano、Toshiaki Taniike

  DOI：10.1039/c7dt02492d

  日期：——

  A series of silsesquioxane-supported Phillips-type molecular catalysts for ethylene polymerization were synthesized by introducing various functional groups in proximity to monoalkylated Cr(III). They were moderately active in ethylene polymerization, while the performance was sensitive to the type of functional group. In particular, the presence of a lone pair near the active center was found to enhance

  通过在单烷基化的Cr（III）附近引入各种官能团，合成了一系列倍半硅氧烷负载的Phillips型乙烯聚合分子催化剂。它们在乙烯聚合中具有中等活性，而性能对官能团的类型敏感。特别地，发现在活性中心附近存在孤对增强了活性并扩展了分子量分布，这可能是由于孤对在时间上捕获了烷基铝。通过添加带有孤对的游离分子从未获得过类似的结果，孤对在活性位点附近的固定是必不可少的。结果表明，基于载体功能化的设计策略可以转移到SiO 2上。负载的铬催化剂。
• Iterative Synthesis of Oligosilanes Using Methoxyphenyl- or Hydrogen-Substituted Silylboronates as Building Blocks: A General Synthetic Method for Complex Oligosilanes
  作者：Takumi Takeuchi、Avijit Roy、Hajime Ito

  DOI：10.1021/jacs.3c05385

  日期：2023.7.26

  transition-metal-catalyzed Si–H borylation reactions. The first key reaction is a cross-Si–Si bond-forming reaction between chloro(oligo)silanes and silylboronates activated by MeLi. The second key reaction is the selective chlorination of the methoxyphenyl group or the hydrogen atom at the terminal of the oligosilanes. Iteration of these two key reactions enables the synthesis of various oligosilanes

  150多年来，有机硅烷因其独特的性能而引起了研究人员的关注，并已成为不可或缺的工业资产。然而，许多合成的具有多个Si-Si键的低聚硅烷相对简单，即它们通常仅包含单个重复单元。更费力的定制合成路线可以产生更复杂的低聚硅烷，但与碳基分子相比，它们的结构多样性仍然有限。开发含有混合取代基的复杂低聚硅烷的有效且实用的合成路线是一个长期存在的挑战。在这里，我们描述了使用甲氧基苯基或氢取代的甲硅烷基硼酸酯迭代合成低聚硅烷，这些硅烷基硼酸酯是通过过渡金属催化的 Si-H 硼化反应获得的。第一个关键反应是由 MeLi 激活的氯（低聚）硅烷和甲硅烷基硼酸酯之间的交叉 Si-Si 键形成反应。第二个关键反应是甲氧基苯基或低聚硅烷末端氢原子的选择性氯化。这两个关键反应的迭代能够合成各种难以获得的低聚硅烷。为了证明这种迭代合成方法的合成效用，通过简单地改变四种不同硅单元的反应顺序来制备具有不同序列的低聚硅烷。此外
• On the [3 + 2] Annulation of Cyclic Allylsilanes with <i>N</i>-Phenyltriazolinedione: An Enantio- and Diastereoselective Synthesis of <i>cis</i>-1,3-Diaminocyclitols
  作者：Raudra T. Dey、Tarun K. Sarkar

  DOI：10.1021/jo100724w

  日期：2010.7.2

  Improved conditions were found to trigger [3 + 2] annulation of cyclic allylsilanes with N-phenyltriazolinedione (PTAD); the products from this reaction were readily tailored into cis-1,3-diaminocyclitols in highly enantioenriched form with full stereochemical control of up to four contiguous stereogenic centers.