4-n-butyl-1-trimethylsilylbenzene | 81631-74-5

• 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: 4-n-butyl-1-trimethylsilylbenzene
• 英文别名: 4-(n-butylphenyl)trimethylsilane；(4-butylphenyl)trimethylsilane；Silane, (4-butylphenyl)trimethyl-；(4-butylphenyl)-trimethylsilane
• CAS: 81631-74-5
• 化学式: C₁₃H₂₂Si
• 分子量: 206.403
• InChiKey: PYXJTAPUYWMANA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.57
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.54
• 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：

  4-n-butyl-1-trimethylsilylbenzene 在 水 作用下， 反应 0.5h， 以91%的产率得到丁苯
  参考文献：
  名称：

  超临界水中有机硅化合物的碳-硅键断裂

  摘要：

  发现芳基硅烷、烯基硅烷、烯丙基硅烷和烷基硅烷在超临界水中发生极其容易和快速的 C-Si 键断裂。即使使用稳定的未活化四烷基硅烷，也会发生快速的 C-Si 键断裂。对照实验揭示了超临界和亚临界条件之间以及超临界水和超临界甲醇之间的巨大差异，证明了超临界水在 C-Si 键断裂中具有独特的反应性。还发现酸，例如 HCl、HBr 和 H 2 SO 4 ，会促进超临界水中的 C-Si 键断裂。

  DOI：

  10.1246/bcsj.77.2071
• 作为产物：
  描述：

  1,4-二溴苯 在 正丁基锂 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 为溶剂， 反应 8.17h， 生成 4-n-butyl-1-trimethylsilylbenzene
  参考文献：
  名称：

  在超临界水中高效快速的 C−Si 键断裂

  摘要：

  发现芳基硅烷、烯基硅烷、烯丙基硅烷和烷基硅烷在超临界水中发生极其容易和快速的 C-Si 键断裂。即使使用稳定的未活化四烷基硅烷，也会发生快速的 C-Si 键断裂。对照实验揭示了超临界和亚临界条件之间以及超临界水和超临界甲醇之间的巨大差异，证明了超临界水在 C-Si 键断裂中具有独特的反应性。

  DOI：

  10.1021/ja034227g

文献信息

• Sodium silylsilanolate enables nickel-catalysed silylation of aryl chlorides
  作者：Kenshiro Hitoshio、Hiroki Yamagishi、Jun Shimokawa、Hideki Yorimitsu

  DOI：10.1039/d1cc02683f

  日期：——

  Structurally diverse aryl chlorides were silylated with sodium silylsilanolate reagents in the presence of a Ni(cod)2 catalyst complexed with a phosphine ligand; PMe2Ph for electron-rich substrates, and PCy2Ph for electron-deficient ones. The mild reaction conditions allowed the silylation of various aryl chlorides including functionalised drug molecules.

  在与膦配体络合的 Ni(cod) 2催化剂存在下，结构多样的芳基氯化物用甲硅烷基硅烷醇钠试剂甲硅烷基化；PMe 2 Ph 用于富电子底物，PCy 2 Ph 用于缺电子底物。温和的反应条件允许包括官能化药物分子在内的各种芳基氯化物进行硅烷化。
• Palladium-Catalyzed Silylation of Aryl Chlorides with Hexamethyldisilane
  作者：Eric McNeill、Timothy E. Barder、Stephen L. Buchwald

  DOI：10.1021/ol701518f

  日期：2007.9.1

  A method for the palladium-catalyzed silylation of aryl chlorides has been developed. The method affords desired product in good yield, is tolerant of a variety of functional groups, and provides access to a wide variety of aryltrimethylsilanes from commercially available aryl chlorides. Additionally, a one-pot procedure that converts aryl chlorides into aryl iodides has been developed.

  已经开发了钯催化的芳基氯甲硅烷基化的方法。该方法以高收率提供所需产物，耐受多种官能团，并提供了从可商购获得的芳基氯化物获得多种芳基三甲基硅烷的途径。另外，已经开发了将芳基氯转化为芳基碘的一锅法。
• Cyclolinear Oligo- and Poly(iminoborane)s: The Missing Link in Inorganic Main-Group Macromolecular Chemistry
  作者：Ozan Ayhan、Nicolas A. Riensch、Clemens Glasmacher、Holger Helten

  DOI：10.1002/chem.201705913

  日期：2018.4.17

  with dichloro‐ or dibromoboranes 2 or 8, respectively. Silicon/boron exchange polycondensation led to oligo(iminoborane)s 11 a,b,ac,d. Alternative synthetic routes to such species involve Sn/B exchange of 1,3‐bis(trimethylstannyl)‐2‐n‐octyl‐1,3,2‐diazaborolidine (16) and n‐C8H17BBr2 (8 a), and the initiated polycondensation of the dormant monomer 14 in the presence of a Brønsted acid (HCl, HOTf, or HNTf2;

  的反应Ñ -C 8 ħ 17 B [N（Me）的森达3 ] 2（1）配有Ñ -C 8 ħ 17的BCl 2（2）得到，而不是直链的聚（iminoborane）时，氨基硼烷Ñ - C 8 H 17 B（Cl）N（Me）SiMe 3（4）和环三聚化后的硼嗪环-（n C 8 H 17 BNMe）3（6）。如果分别将1,3-双（三甲基甲硅烷基）-1,3,2-二氮杂硼烷核苷7与二氯或二溴硼烷2或8一起用作共聚单体，则可有效抑制导致硼嗪形成的副反应。硅/硼交换缩聚导致低聚（亚氨基硼烷）s 11 a，b，ac，d。此类物种的替代合成路线涉及1,3-双（三甲基锡烷基）-2 - n-辛基-1,3,2-二氮杂硼烷（16）和n- C 8 H 17 BBr 2（8 a的Sn / B交换），并在布朗斯台德酸（HCl，HOTf或HNTf 2； Tf =三氟甲基磺酰基）的存在下引发休眠单体14的缩聚反应。尽管尝试获得带
• Efficient and Facile Ar−Si Bond Cleavage by Montmorillonite KSF:  Synthetic and Mechanistic Aspects of Solvent-Free Protodesilylation Studied by Solution and Solid-State MAS NMR
  作者：Yossi Zafrani、Eytan Gershonov、Ishay Columbus

  DOI：10.1021/jo0706170

  日期：2007.8.31

  A facile and efficient method for the cleavage of the Ar−Si bond of various aryl trimethyl silanes is described. When adsorbed on montmorillonite KSF (mont KSF), these arylsilanes readily undergo a solvent-free protodesilylation to the corresponding arenes at room temperature in excellent yields. This approach seems to be superior to the traditional mild methods (i.e., desilylation by TFA, TBAF, CsF)

  描述了一种用于裂解各种芳基三甲基硅烷的Ar-Si键的简便有效的方法。当这些芳基硅烷吸附在蒙脱土KSF（mont KSF）上时，很容易在室温下以优异的收率将无溶剂的原甲硅烷基化反应生成相应的芳烃。就反应收率，反应速率和环境条件而言，这种方法似乎优于传统的温和方法（即，TFA，TBAF，CsF进行的甲硅烷基化）。还介绍了一些使用溶液和固态幻角旋转（SS MAS）1 H NMR进行的机理研究。
• Synthesis and Characterization of Lewis Base-Free, σ-Bonded Lithium Aryls:  A Structural Model for Unsolvated Phenyllithium in the Solid State
  作者：Rudolf J. Wehmschulte、Philip P. Power

  DOI：10.1021/ja962889i

  日期：1997.3.1

  The synthesis and characterization of four Lewis base-free, sigma-bonded lithium aryls are reported. This work was undertaken in order to provide a model for the solid-state structure of phenyllithium, which is currently unknown. Nondonor hydrocarbon solubility of the four lithium aryls (LiC6H3-3,5-t-Bu(2))(6) (1), (LiC6H4-4-t-Bu)(n) (2), (LiC6H4-4-n-Bu)(n) (3), and LiC6H4-4-SiMe(2)(t-Bu)}(n) (4) was achieved by the incorporation of meta- or para-substituents on the aryl rings. This permitted C-13 NMR spectroscopy and crystal growth using their solutions. It is proposed that the absence of bulky ortho-substituents allows association of the Lithium aryls to occur in a manner similar to that of phenyllithium itself. The C-13 NMR data for the ipso-carbon atoms suggest an association number of at least four or, more probably, six in solution. These data are in agreement with the X-ray crystal structure of 1, which is hexameric, with a distorted octahedral (trigonal antiprismatic) array of lithium ions. Six of the eight Lis faces are capped by an aryl group that interacts primarily through the C(ipso) atom. Weaker Li-C(ortho) interactions are also apparent. This structure is the first of this type for an unsolvated, sigma-bonded Lithium aryl. Crystal data with Cu K alpha (lambda = 1.541 78 Angstrom) radiation for 1 at 130 K: 1, C84H126Li6, M = 1177.49, a = 13.516(2) Angstrom, b = 15.124(3) Angstrom, c = 20.958(3) Angstrom, alpha = 84.084(13)degrees, beta = 86.249(11) Angstrom, gamma = 68.675(13)degrees, V = 3967.7(11) Angstrom(3), Z = 2, space group , R(1) = 0.085 for 7983 (I > 2 sigma(I)) data.