trimethylsilane | 37891-39-7

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: trimethylsilane
• 英文别名: bis(phenylthio)(trimethylsilyl)methane；bis(phenylthio)trimethylsilylmethane；Bis(phenylthio)-trimethylsilylmethan；Silylthioacetal (3)；Silane, [bis(phenylthio)methyl]trimethyl-；bis(phenylsulfanyl)methyl-trimethylsilane
• CAS: 37891-39-7
• 化学式: C₁₆H₂₀S₂Si
• 分子量: 304.552
• InChiKey: HPYOLIQEFJCHSW-UHFFFAOYSA-N

物化性质

• 沸点：
  380.7±32.0 °C(Predicted)
• 密度：
  1.08±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.77
• 重原子数：
  19
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  50.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  trimethylsilane 在 正丁基锂 、 氧气 、 四乙基对甲苯磺酸铵 作用下， 以 四氢呋喃 、 正己烷 、 溶剂黄146 为溶剂， 反应 4.0h， 生成 S-Phenyl 2-(phenylthio)nonanethioate
  参考文献：
  名称：

  Electroinitiated oxygenation of alkenyl sulfides and alkynes in the presence of thiophenol

  摘要：

  Electrolysis of alkenyl sulfides in the presence of thiophenol with bubbling of molecular oxygen gave the corresponding alpha-(phenylthio) carbonyl compounds with the consumption of a catalytic amount of electricity. An electroinitiated radical chain mechanism has been proposed. The reaction also took place without electrochemical initiation, but much (5-50 times) longer reaction time was required for the completion of the reaction. The potential utility of the present reaction in organic synthesis is demonstrated by the net 1,2-transposition of a phenylthio group and a carbonyl group. The electroinitiated oxygenation of ketene dithioacetals also proceeded smoothly to give the corresponding alpha-(phenylthio) thiol esters. It was also found that the electroinitiated oxygenation of alkynes in the presence of thiophenol gave alpha-(phenylthio) carbonyl compounds. A mechanism involving the initial formation of alkenyl sulfides has been proposed.

  DOI：

  10.1021/jo00070a021
• 作为产物：
  描述：

  苯次磺酰氯 以75%的产率得到
  参考文献：
  名称：

  AGER D. J., TETRAHEDRON LETT., 1981, 22, NO 29, 2803-2806

  摘要：

  DOI：

文献信息

• Yield and selectivity enhancement by trimethylsilyl chloride in the conjugate addition of stabilized organolithiums
  作者：Hong Liu、Theodore Cohen

  DOI：10.1016/0040-4039(95)01919-9

  日期：1995.12

  The yield and selectivity in the conjugate addition of some stabilized organolithiums to α,β-unsaturated carbonyl compounds, especially easily polymerized ones, are increased in the presence of trimethylsilyl chloride, alone or in combination with hexamethylphosphoric triamide. E-silyl enol ethers bearing the versatile phenylthio group are obtained prior to hydrolysis. Some synthetic uses are demonstrated

  在三甲基甲硅烷基氯的存在下，单独或与六甲基磷酸三酰胺结合使用，可以稳定地将某些稳定的有机锂共轭添加到α，β-不饱和羰基化合物中，尤其是易于聚合的化合物中，从而提高收率和选择性。在水解之前，获得带有通用的苯硫基的E-甲硅烷基烯醇醚。证明了一些合成用途。
• The synthesis of ketones viaα-silyl sulphides
  作者：David J. Ager

  DOI：10.1039/p19860000195

  日期：——

  an alkyl- lithium to 1-phenylthio-1-trimethylsilylethene (7), and transmetallation of a tributylstannyl moiety. The formation of an alkyl-lithium by reaction of lithium naphthalenide with a phenyl sulphide provided an additional route to (2) from bis(phenylthio)acetals (8). An alternative path to the α-phenylthiosilanes (2) was to reduce the corresponding α-phenylsulphonylsilane (15); these, in turn

  α-苯硫基硅烷（2）已经通过衍生自1-苯硫基-1-三甲基甲硅烷基烷（1）的阴离子（4）的烷基化而制备。这些阴离子（4）已经通过多种方法制备，包括：（1）的直接去质子化，萘锂置换苯硫基，在1-苯基硫-1-三甲基甲硅烷基乙烯中添加烷基锂（7），以及三丁基锡烷基部分的金属转移。通过萘二甲酸锂与苯硫醚的反应形成烷基锂，提供了从双（苯硫基）缩醛（8）到（2）的另一条路线。α-苯基硫代硅烷的替代途径（2）是还原相应的α-苯基磺酰基硅烷（15）; 这些反过来很容易从α-磺酰基阴离子的烷基化或甲硅烷基化获得。通过sila-Pummerer重排将α-苯基硫代硅烷（2）转化为O-三甲基甲硅烷基苯基硫代缩醛（18），尽管在某些情况下这会因硫化乙烯基（20）的形成而变得复杂。随后将（18）和（20）水解，得到酮（3）。
• Stereocontrolled double ring expansion of fused allylidenecyclopropanes. A novel route to hydroazulenes and other fused bicyclic systems
  作者：Craig A. Shook、Matthew L. Romberger、Sang Hun Jung、Manchao Xiao、James P. Sherbine、Birong Zhang、Fu Tyan Lin、Theodore Cohen

  DOI：10.1021/ja00076a037

  日期：1993.11

  A variety of 1-(phenylthio)-1-(trimethylsilyl)cyclopropanes, fused to five-, six-, and seven-membered rings have been prepared by several procedures and reductively lithiated by means of aromatic radical anions. The resulting 1-lithio-1-(trimethylsilyl)cyclopropanes have been treated in most cases with α,β-unsaturated aldehydes, followed by potassium tert-butoxide to yield allylidenecyclopropanes.

  多种 1-（苯硫基）-1-（三甲基甲硅烷基）环丙烷与五、六和七元环稠合已通过多种方法制备，并通过芳香基阴离子还原锂化。在大多数情况下，所得的 1-锂硫基-1-（三甲基甲硅烷基）环丙烷已用 α,β-不饱和醛处理，然后用叔丁醇钾处理，生成烯丙基环丙烷。后者在密封管或闪蒸真空热解装置中进行热重排后，会发生双环膨胀，生成环戊烯环己烯、-环庚烯（氢化茚）或-环辛烯
• Alkyl- and arylsubstituted ketenedithioacetal tetroxides: Diels-alder reactivity and reductive desulfonylation of the adducts
  作者：Ottorino De Lucchi、Davide Fabbri、Vittorio Lucchini

  DOI：10.1016/s0040-4020(01)92236-7

  日期：1992.2

  M lithium perchlorate under sonication. Under these reaction conditions, the cycloaddition to quadricyclane, 1-methoxy-, 1- and 2-trimethylsilyloxy-1,3-butadiene and to the Danishefsky diene were investigated. In the cycloaddition to 1-trimethylsilyloxy-1,3-butadiene and to the Danishefsky diene the open chain adducts (Z)- 14 and 17 were obtained in high yield as primary adducts. Eventually, the former

  报告了通式1的代表性烷基和芳基取代的烯二硫缩醛四氧化物的Diels-Alder反应性。这些亲双烯体在热条件下（回流甲苯）与环戊二烯反应，主要得到内加合物。在1C和1D的情况下，根据nOe实验确定，相对于联苯或联萘残基而言，形成的内和外加合物具有完全的立体选择性。亲双烯体1A-D未能在相似的反应条件下与其他二烯反应，但在超声处理下在含5 M高氯酸锂的乙醚中有效反应。在这些反应条件下，研究了四环烷，1-甲氧基-，1-和2-三甲基甲硅烷氧基-1,3-丁二烯和Danishefsky二烯的环加成反应。在1-三甲基甲硅烷氧基-1，3-丁二烯和Danishefsky二烯的环加成中，以高收率获得作为主加合物的开链加合物（Z）-14和17。最终，前者经历异构化为（E）-14，而后者进一步水解为18。开链化合物19也通过12Ac的碱处理获得。高度稳定的双（苯磺酰基）取代的碳负离子的产生可能是这些转变的驱动力。
• Transformation of α-assisted carbanions into the corresponding trimethylsiloxy derivatives using bis(trimethylsilyl)peroxide
  作者：P. Dembech、A. Guerrini、A. Ricci、G. Seconi、M. Taddei

  DOI：10.1016/s0040-4020(01)88391-5

  日期：1990.1

  The reaction of bis(trimethylsilyl)peroxide with tlithium derivatives of sulphides and nitriles is reported to give the corresponding O-trimethylsilyl hemithioacetals and cyanohydrins. From these products the carbonyl function can be exposed in acidic media or in the presence of fluoride ions. This methodology provides an attractive route to transform a CH2-X group (X = PhS, MeS or CN) into the corresponding

  据报道，双（三甲基甲硅烷基）过氧化物与硫化物和腈的锂衍生物反应生成相应的O-三甲基甲硅烷基半硫缩醛和氰醇。从这些产物中，羰基官能团可以在酸性介质中或在氟离子存在下暴露。这种方法学提供了一种有吸引力的途径，可以将CH 2 -X基团（X = PhS，MeS或CN）转化为相应的CHO，从而可以制备认为难以制备的醛，例如生成的甲酰基三甲基硅烷并使用维蒂希反应原位捕获。