三甲基-(苯基-三甲基硅烷基-甲基)硅烷 | 14595-77-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 三甲基-(苯基-三甲基硅烷基-甲基)硅烷
• 英文名称: bis(trimethylsilyl)phenylmethane
• 英文别名: (phenylmethylene)bis(trimethylsilane)；α,α-Bis-(trimethylsilyl)-toluol；phenylbis(trimethylsilyl)methane；α,α-bis(trimethylsilyl)toluene；Silane, (phenylmethylene)bis(trimethyl-；trimethyl-[phenyl(trimethylsilyl)methyl]silane
• CAS: 14595-77-8
• 化学式: C₁₃H₂₄Si₂
• 分子量: 236.505
• InChiKey: NISUIYZIODIZTR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.53
• 重原子数：
  15
• 可旋转键数：
  3
• 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

安全信息

• 海关编码：
  2931900090

反应信息

• 作为反应物：
  描述：

  三甲基-(苯基-三甲基硅烷基-甲基)硅烷 在 正丁基锂 、 四甲基乙二胺 作用下， 以 正己烷 为溶剂， 反应 116.0h， 生成 1,2-bis(trimethylsilyl)-1,2-diphenylethane
  参考文献：
  名称：

  1，甲硅烷基取代的有机锂化合物的重排中的n-三有机甲硅烷基迁移

  摘要：

  DOI：

  10.1016/s0022-328x(00)86806-0
• 作为产物：
  描述：

  在 二苯基甲烷 作用下， 以 四氢呋喃 为溶剂， 生成 三甲基-(苯基-三甲基硅烷基-甲基)硅烷
  参考文献：
  名称：

  Carbon acidity. 77. Ion pair carbon acidities of some silanes in tetrahydrofuran

  摘要：

  The relative solvent-separated ion pair (SSIP) lithium acidity (PK(Li)/THF) and contact ion pair (CIP) cesium acidity (pK(Cs/THF)) were obtained for 9-fluorenyltrimethylsilane (1) (21.3, 21.6, respectively) and 9-fluorenyl-tert-butyldimethylsilane (2) (20.3, 20.6, respectively) in THF. Values for pK(Cs/THF) were determined at 25-degrees-C for (p-biphenylylmethyl)-tert-butyldimethylsilane (3), 35.4, benzyltrimethylsilane (4), 37.5, alpha,alpha-bis(trimethylsilyl)toluene (5), 34.1, 2-(trimethylsilyl)-1,3-dithiane (6), 33.5, (trimethylsilyl)acetonitrile (7), 28.8, and tris(trimethylsilyl)methane (8), 36.8. Some thermodynamic parameters were determined by measurements at other temperatures, and some ionic acidities (pK(FI)) were determined by conductivity studies. Carbanion stabilization by these silyl substituents varies from about 1 to over 3 pK units in different systems. 9,9-Bis(trimethylsilyl)fluorene (9) was found to undergo silyl transfer on treatment with various carbanions, but this reaction is slower than proton transfer.

  DOI：

  10.1021/jo00059a031

文献信息

• Novel Syntheses of 1, 2-Diarylacetylenes and α-Silylalcohols from Acylsilanes Mediated by Ytterbium Metal
  作者：Yuki Taniguchi、Nobuto Fujii、Yoshikazu Makioka、Ken Takaki、Yuzo Fujiwara

  DOI：10.1246/cl.1993.1165

  日期：1993.7

  Aromatic acylsilanes such as benzoyltrimethylsilane react with ytterbium metal to give symmetrical 1,2-diarylacetylenes in good yields. Aliphatic acylsilanes are reduced with lanthanoid reagents such as Yb metal and SmI2 to afford α-silylalcohols.

  具有香味的酰基硅烷，如苯甲酰基三甲基硅烷，与镱金属反应后能以良好产率得到对称的1,2-二芳基乙炔。脂肪族酰基硅烷通过镱金属或二碘化钐等镧系试剂还原，能够得到α-硅基醇。
• Organosilicon compounds
  作者：M.A. Cook、C. Eaborn、D.R.M. Walton

  DOI：10.1016/s0022-328x(00)85286-9

  日期：1971.6

  The compounds (Me3Si)xCH(3−x)Cl (x = 1–3), (Me3Si)xCH(3−x)Br (x = 1, 3) and Me3SiCMe2Br have been found to react with 90% acetone or 80% ethanol at 70° at rates too small for convenient measurement. Towards aqueous acetone, the compound PhMe(Me3Si)CBr is 110 times less reactive at 50° than PhMe2CBr at 0°. It is concluded that relative to α-Me, α-t-Bu or α-Me3Si groups decrease the ease of formation

  （Me 3 Si）x CH （3- x） Cl（x = 1-3），（Me 3 Si）x CH （3- x） Br（x = 1，3）和Me 3 SiCMe 2 Br的化合物具有已发现在70°下会与90％丙酮或80％乙醇以太小的速率反应，无法方便地进行测量。对于丙酮水溶液，化合物PhMe（Me 3 Si）CBr在50°时的反应活性比在0°时的PhMe 2 CBr低110倍。可以得出结论，相对于α-ME，α -叔-卜或α-ME 3 Si基团降低容易形成碳离子的。
• The electron-releasing effects of mono-, bis-, and tris-(trimethylsilyl)methyl groups. The importance of hyperconjugation in the electronic effects of α-metalloalkyl groups
  作者：A.R. Bassindale、C. Eaborn、D.R.M. Walton、D.J. Young

  DOI：10.1016/s0022-328x(00)80087-x

  日期：1969.11

  release by the (Me3Si)xCH3-x groups, increase in the order x = 0 < 3 < 1 < 2 for both the m- and p-compounds. The 19F chemical shifts in the p-(Me3Si)3CH3-xC6H4F compounds indicate the same order of electron release. This order is not consistent with attribution of effects of the (Me3Si)xCH3-x groups entirely or even primarily to inductive release of electrons by the Me3Si groups, but is consistent with

  高氯酸甲醇水溶液对（Me 3 Si）x CH 3- x C 6 H 4 SiMe 3化合物中芳基-Si键的裂解速率，以及因此由（Me 3 Si）x CH 3-释放的电子x个组，对于m-和p-化合物，按x = 0 <3 <1 <2的顺序增加。p-（Me 3 Si）3 CH 3- x C 6 H 4中的19 F化学位移F化合物表示电子释放的顺序相同。这个命令是不与的（ME的效果归因一致3 Si）的X CH 3- X基团完全或甚至主要由ME电子感应释放3 Si基团，但是与从ME电子hyperconjugative释放一致3 Si-C键。
• Stereoselective Peterson Olefinations from Bench-Stable Reagents and<i>N</i>-Phenyl Imines
  作者：Manas Das、Atul Manvar、Maïwenn Jacolot、Marco Blangetti、Roderick C. Jones、Donal F. O'Shea

  DOI：10.1002/chem.201500475

  日期：2015.6.8

  The synthesis of bench‐stable α,α‐bis(trimethylsilyl)toluenes and tris(trimethylsilyl)methane is described and their use in stereoselective Peterson olefinations has been achieved with a wide substrate scope. Product stereoselectivity was poor with carbonyl electrophiles (E/Z ∼1:1 to 4:1) though this was significantly improved by employing the corresponding substituted N‐benzylideneaniline (up to 99:1)

  描述了台稳的α，α-双（三甲基甲硅烷基）甲苯和三（三甲基甲硅烷基）甲烷的合成，并已在较宽的底物范围内实现了它们在立体选择性Peterson烯烃中的应用。羰基亲电试剂的产物立体选择性差（E / Z约为1：1至4：1），尽管通过使用相应的取代N-苄叉基苯胺（最高达99：1）作为替代亲电试剂可以显着改善。烯化副产物被鉴定为N，N-双（三甲基甲硅烷基）苯胺，很容易通过酸水萃取从产物中分离出来。已经获得了自催化循环的证据。
• <i>Z</i>-Stereoselective Aza-Peterson Olefinations with Bis(trimethylsilane) Reagents and Sulfinyl Imines
  作者：Manas Das、Donal F. O’Shea

  DOI：10.1021/acs.orglett.5b03519

  日期：2016.1.15

  Highly stereoselective aza-Peterson olefinations from bench-stable α,α-bis(trimethylsilyl)toluene reagents and N-substituted imines have been achieved using TMSO–/Bu4N+ as Lewis base activator in THF. Remarkably, and for the first time, N-t-butanesulfinyl imines were utilized for the synthesis of Z-stilbenes with excellent selectivities, while N-aryl imines generated E-stilbenes under identical reaction

  从台式稳定α，α-双（三甲硅烷基）甲苯试剂和N-取代的亚胺高度立体选择性氮杂彼得森烯化反应已经使用TMSO实现- /卜4 Ñ +在THF作为路易斯碱的活化剂。值得注意的是，和在第一次，ñ -吨-butanesulfinyl亚胺被用于合成Ž -stilbenes具有优良的选择性，而Ñ -芳基生成亚胺ë相同的反应条件下-stilbenes。该协议已证明对于形成低分子量副产物的许多实例而言是通用的。的Z选择性的原点建议成为非对映选择性加成到的结果ñ -吨-butanesulfinyl亚胺随后顺原位形成的高价硅酸盐的β-消除。