trimethylsilane | 115505-16-3

• 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: trimethylsilane
• 英文别名: bromo[methoxy(trimethylsilyl)]methane；bromo(methoxy)methyltrimethylsilane；[Bromo(methoxy)methyl]-trimethylsilane
• CAS: 115505-16-3
• 化学式: C₅H₁₃BrOSi
• 分子量: 197.147
• InChiKey: MQYMEGYOIOYRPO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.23
• 重原子数：
  8
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 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：

  trimethylsilane 、 正丁醇 在 N,N-二异丙基乙胺 作用下， 生成 [Butoxy(methoxy)methyl]-trimethylsilane
  参考文献：
  名称：

  2-Trimethylsilyl-1,3-dithiolane as a masked dithiolane anion

  摘要：

  2-Trimethylsilyl-1,3 -dithiolane, easily obtainable through transthioacetalization of corresponding silylated acetals, can be efficiently reacted, under fluoride-ion catalysis, with different organic electrophiles, leading to a general and mild functionalization protocol. This reactivity discloses the ability of compound 3 to act as a masked dithiolane anion. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(01)00771-7
• 作为产物：
  描述：

  (甲氧基甲基)三甲基硅烷 在 N-溴代丁二酰亚胺(NBS) 、 偶氮二异丁腈 作用下， 以 四氯化碳 为溶剂， 生成 trimethylsilane
  参考文献：
  名称：

  分子内参与烷氧基碳鎓离子池。

  摘要：

  [反应：见正文]通过在适当位置引入醚基，阳离子碳上没有取代基的烷氧碳鎓离子已积累为“阳离子池”。建议醚氧的分子内参与负责烷氧基碳鎓离子的稳定。

  DOI：

  10.1021/ol051915r

文献信息

• Stereoselective Functionalization of Dithiolanes and Dithianes: The First Example of an Axial Trapping
  作者：Alessandro Degl’Innocenti、Salvatore Pollicino、Antonella Capperucci、Vanda Cerè、Tiziano Nocentini

  DOI：10.1055/s-2002-33521

  日期：——

  and dithianes can be easily functionalized under fluoride ion conditions. The functionalization occurs stereoselectively, the products bearing the incoming groups in the position formerly occupied by the silyl moiety. These results lead to the first example of dithiolane and dithiane axial trapping.

  2-Silyl-1,3-dithiolanes 和 dithianes 在氟离子条件下很容易被官能化。官能化立体选择性地发生，产物在先前由甲硅烷基部分占据的位置上带有传入基团。这些结果导致了二硫戊环和二噻烷轴向捕获的第一个例子。
• Synthesis of A New Class of Sulfurated and Selenated Silyl Heterocycles
  作者：Antonella Capperucci、Damiano Tanini、Alessandro Degl’Innocenti

  DOI：10.1080/10426507.2012.727518

  日期：2013.4.1

  Abstract 2-Trimethylsilyl-1,3-thiaselenolanes and 2-trimethylsilyl-1,3-oxaselenolanes can be accessed through the reaction of a silyl acetal with β-mercapto- and β-hydroxyselenols under Lewis acid conditions. GRAPHICAL ABSTRACT

  摘要 2-Trimethylsilyl-1,3-thiaselenolanes 和2-trimethylsilyl-1,3-oxaselenolanes 可以通过甲硅烷基缩醛与β-巯基-和β-羟基硒醇在路易斯酸条件下反应获得。图形概要
• Intramolecular Participation in Alkoxycarbenium Ion Pools
  作者：Seiji Suga、Shinkiti Suzuki、Jun-ichi Yoshida

  DOI：10.1021/ol051915r

  日期：2005.10.1

  [reaction: see text] Alkoxycarbenium ions having no substituents on the cationic carbon have been accumulated as "cation pools" by the introduction of an ether group in an appropriate position. Intramolecular participation of the ether oxygen is suggested to be responsible for stabilization of the alkoxycarbenium ions.

  [反应：见正文]通过在适当位置引入醚基，阳离子碳上没有取代基的烷氧碳鎓离子已积累为“阳离子池”。建议醚氧的分子内参与负责烷氧基碳鎓离子的稳定。
• Intramolecular Behaviors of Anthryldicarbenic Systems:  Dibenzo[<i>b</i>,<i>f</i>]pentalene and 1<i>H</i>,5<i>H</i>-Dicyclobuta[<i>d</i><i>e,kl</i>]anthracene
  作者：J. Kirby Kendall、Harold Shechter

  DOI：10.1021/jo010404p

  日期：2001.10.1

  9,10-Bis[methoxy(trimethylsilyl)methyl]anthracenes (24), synthesized from 9,10-dilithioanthracene (26) and bromomethoxytrimethylsilylmethane (27, 2 equiv), decompose (550-650 degreesC/10(-3) mmHg) carbenically to dibenzo[b,f]pentalene (28, > 48%). 9,10-Anthryldicarbenes 39 or their equivalents convert to pentalene 28 rather than di-peri-cyclobutanthracenes 30 and 31, benzobiphenylene 32, or extended rearrangement products 33-38. Formation of 28 from 24 raises questions with respect to the behavior of 1,3,4,6-cycloheptatetraenyl-1-carbenes 49, 2,4,5,7-cyclooctatetraenylidene 51, 2,5,7-cyclooetatriene-1,4-diylidene 52, 1,2,4,5,7-cyclooetapentaene 53, and bicyclo[4.1.0]heptatrienyl-1-carbenes 54 and to carbon-skeleton and hydrogen rearrangements of anthryldicarbenes 39 and/or their equivalents at various temperatures. 1,5-Bis [methoxy(trimethylsilyl)methyl] anthracenes (25), prepared from 1,5-diiodoanthracene (63) and methoxytrimethylsilylmethylzinc bromide (57,2 equiv) as catalyzed by PdCl2(PPh3)(2), yield the di-peri-carbenic reaction product 1H,5H-dicyclobuta[de,kl]-anthracene (30, > 40%) on pyrolysis at 550-650 degreesC/10(-3) mmHg. Proof of structure and various aspects of the mechanisms of formation of 30 are discussed.
• Preparative Methodology and Pyrolytic Behavior of Anthrylmonocarbenes:  Synthesis and Chemistry of 1<i>H</i>-Cyclobuta[<i>de</i>]anthracene
  作者：J. Kirby Kendall、Thomas A. Engler、Harold Shechter

  DOI：10.1021/jo981105b

  日期：1999.6.1

  This study involves (1) the behavior of organolithium reagents (1-6), (2) development of efficient methods for preparing 9(7)- and 1(8)-[methoxy(trimethylsilyl)methyl] anthracenes and their analogues, (3) the intramolecular chemistry of the 9(9)- and 1(l0)-anthrylcarbenes generated by pyrolyses of 7 and 8, respectively, and (4) investigation of thermal behavior and bromination of the 1H-cyclobuta[de]anthracene (11) obtained from 9 or 10. alpha-Methoxy-9-anthrylmethyllithium (1), prepared from 9-(methoxymethyl)anthracene (14) and t-BuLi in TMEDA/Et2O/pentane, reacts at C-10 with D2O, chlorotrimethylsilane, dimethyl sulfate, benzoyl chloride, acetaldehyde, benzaldehyde, and acetone to give, after neutralization, 9,10-dihydro-9-(methoxymethylene)-10-substituted- anthracenes 15 and 21a-f. However, lithiation of 9-(thiomethoxymethyl)anthracene (25) with t-BuLi/TMEDA/Et2O/pentane occurs by an apparent radical-anion displacement process to give 9-anthrylmethyllithium (3), which then reacts with chlorotrimethylsilane to yield 9-(trimethylsilylmethyl)anthracene (28). Similarly, 28 is formed from 25 and from 9-(trimethylsilyloxymethyl)-anthracene (29) with lithium and then chlorotrimethylsilane. The electrophiles D2O, dimethyl sulfate, and benzaldehyde react with 3 at its methyl and its C-10 positions. [Methoxy(trimethylsilyl)methyl]arenes 40-42 and 7 are obtained by reactions of their aryllithium and arylmagnesium bromide precursors with bromo(methoxy)methyltrimethylsilane (39). 1-(Methoxymethyl)anthracene (45) is converted conveniently by t-BuLi and chlorotrimethylsilane to 8. Flash-vacuum pyrolyses of 7 and 8 yield 11 preparatively; 11 then thermolyzes to 2H-cyclopenta[jk]fluorene (46). Decomposition of 9-deuterio-10-[methoxy(trimethylsilyl)methyl]anthracene (55) at 650 degrees C/10(-3) mm results in 10(56)- and 1(57)-deuteriocyclobutanthracenes, thus revealing that the 10-deuterio-9-anthrylcarbene inserts to give 56 and also isomerizes extensively before yielding 57. Of note is that 56 isomerizes thermally by C-10-D movement to form 2-deuteriocyclopentafluorene 58, 57 rearranges by Clo-H movement to yield deuteriocyclopentafluorene 59, and 58 and 59 equilibrate 1,5-sigmatropically. Possible mechanisms for the isomerizations of 56 and 57 are outlined. Further, bromine adds rapidly to 11 to form 9,10-dibromo-9,10-dihydro-1H-cyclobuta[de]anthracene (94), which eliminates HBr on warming to yield 10-bromo-1H-cyclobuta[de]anthracene (95).