trimethylsiloxide anion | 41866-81-3

• 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: trimethylsiloxide anion
• 英文别名: trimethylsiloxide ion；trimethylsilanolate；Me3SiO(1-)；[SIMe3O]-；trimethyl(oxido)silane
• CAS: 41866-81-3
• 化学式: C₃H₉OSi
• 分子量: 89.1894
• InChiKey: LFPXTSYMGPLZQV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.18
• 重原子数：
  5
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  23.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  trimethylsiloxide anion 生成 苯氧基自由基
  参考文献：
  名称：

  LUKYANENKO, L. V.;PETRENKO, V. V.;TUROVSKIJ, A. A.;TUROVSKIJ, N. A., ZH. ORGAN. XIMII, 1982, 18, N 4, 705-708

  摘要：

  DOI：
• 作为产物：
  描述：

  三甲基乙氧基硅烷 在 三氟化氮 作用下， 生成 trimethylsiloxide anion
  参考文献：
  名称：

  气相中氧化硅离子的甲基-氟顺序交换反应

  摘要：

  用我交换氟：在气相中存在NF 3的三甲基氧化硅离子经历了不寻常的顺序复分解型反应，其中甲基被氟交换。理论计算表明，该反应是通过三步内部亲核置换机制进行的，该机制以五配位硅酸酯物质（参见图片）为过渡态而非中间体为特征。

  DOI：

  10.1002/anie.201203970
• 作为试剂：
  描述：

  2-碘苯甲酸甲酯 在 copper(l) iodide 、 bis(triphenylphosphine)palladium(II)-chloride 、 dirhodium(II) tetrakis(perfluorobutyrate) 、 三苯基膦 trimethylsiloxide anion 、 三乙胺 、 氯甲酸甲酯 作用下， 以 二氯甲烷 为溶剂， 反应 16.5h， 生成 2-<(2,3-dihydro-1-oxo-1H-3-indenylidene)methyl>-2,3,4,5-tetrahydrofuran
  参考文献：
  名称：

  Rhodium(II)-catalyzed cyclization reactions of alkynyl-substituted .alpha.-diazo ketones

  摘要：

  Treatment of several omicron-alkynl-substituted alpha-diazoacetophenone derivatives with rhodium (II) carboxylates results in the formation of substituted indenones. The simplest mechanism accounting for the results involves addition of a rhodium-stabilized carbenoid onto the acetylenic pi-bond to generate a vinyl carbenoid directly of possibly a highly strained cyclopropene derivative. The vinyl carbenoid was found to undergo addition to a neighboring alkene tethered on the side chain to give an indenyl-substituted bicyclo[3.1.0]hexane derivative. A number of related systems were examined so as to probe the scope and generality of the process. Treatment of omicron-(6,8-nonadien-1-ynyl)-alpha-diazoacetophenone with rhodium (II) mandelate afforded a cyclopent[g]azulenone derivative. The formation of this compound involves a divinylcyclopropane intermediate that readily undergoes a Cope rearrangement under the reaction conditions. The rhodium-catalyzed reaction of 2-(6-oxo-1-hepty-nyl)-alpha-diazoacetophenone in the presence of N-phenylmaleimide afforded a mixture of two cycloadducts. One of the products can be accounted for in terms of a cyclization of the vinyl carbenoid onto the oxygen atom of the neighboring carbonyl group to give a resonance-stabilized dipole. 1,3-Dipolar cycloaddition of the carbonyl ylide across the activated pi-bond of N-phenylmaleimide affords the observed product. The second cycloadduct is formed by a 1,2-hydrogen shift of the initially produced vinyl carbenoid. The resulting diene undergoes a subsequent Diels-Alder reactions with N-phenylmaleimide.

  DOI：

  10.1021/jo00007a047

文献信息

• Gas-phase reaction of silyl and trimethylsilyl anions. The formation of silicon-oxygen and silicon-sulfur bonds. A flowing afterglow and ab initio study
  作者：John C. Sheldon、John H. Bowie、Charles H. DePuy、Robert. Damrauer

  DOI：10.1021/ja00281a055

  日期：1986.10

  Les ions H 3 Si − et Me 3 Si − reagissent avec CO 2 , COS, CS 2 , SO 2 , N 2 O, MeNCO et MeNCS formant H 3 SiO − , Me 3 SiO − , Me 3 SiO − , H 3 SiS − ou Me 3 SiS − . Cinetique

  Les 离子 H 3 Si - et Me 3 Si - reagissent CO 2 , COS, CS 2 , SO 2 , N 2 O, MeNCO et MeNCS共振峰 H 3 SiO - , Me 3 SiO - , Me 3 SiO - , H 3 SiS - ou Me 3 SiS - 。电影
• Gas-phase reactions of anions with substituted silanes
  作者：C. H. DePuy、Veronica M. Bierbaum、L. A. Flippin、Joseph J. Grabowski、Gary K. King、Robert J. Schmitt、S. A. Sullivan

  DOI：10.1021/ja00535a031

  日期：1980.7

  fluoride, amide, hydroxide, and methoxide ions with a variety of substituted silanes have been studied by the flowing afterglow technique. Fluoride reacts readily with trimethylsilyl derivatives to displace benzyl, alkenyl, and alkynyl anions. These reactions have also been used to generate specific structural isomers (CH3C=C" and CH2=C=CH"). Anions more basic than phenide ion cannot be produced in this

  通过流动余辉技术研究了氟化物、酰胺、氢氧化物和甲醇离子与各种取代硅烷的气相反应。氟化物很容易与三甲基甲硅烷基衍生物反应以取代苄基、烯基和炔基阴离子。这些反应也已用于生成特定的结构异构体（CH3C=C" 和 CH2=C=CH"）。比苯阴离子更碱性的阴离子不能以这种方式产生，它们的母体三甲基硅烷通过更复杂的机制与氟化物相互作用。每当存在酸性氢时，酰胺、氢氧化物和甲醇离子通过置换和质子提取与取代的三甲基硅烷反应；在没有可置换基团和酸性氢的情况下，酰胺、氢氧化物和甲醇盐的反应与氟离子的反应平行。出现了。我们一直在使用流动的余辉系统进行此类实验。5,6 一个直接的问题涉及在气相中形成碳负离子的方法，因为只有相对少数的阴离子可以通过电子捕获有效地形成。因此，大多数有机阴离子是通过强气相碱（如 CH3O"、OH" 或 NH2"）从中性有机化合物中转移质子生成的。在许多情况下，这是一种有效且明确的方法，并
• The gas-phase acidities of the alkanes
  作者：Charles H. DePuy、Scott Gronert、Stephan E. Barlow、Veronica M. Bierbaum、Robert Damrauer

  DOI：10.1021/ja00188a003

  日期：1989.3

  acidities of 15 simple alkanes have been determined in a flowing afterglow-selected ion flow tube (FA-SIFT) by a kinetic method in which alkyltrimethylsilanes were allowed to react with hydroxide ions to produce a mixture of trimethylsiloxide ions by loss of alkane and alkyldimethylsiloxide ions by loss of methane. The reaction is proposed to proceed by addition of hydroxide ion to the silane to form

  在流动余辉选择离子流管 (FA-SIFT) 中，通过动力学方法测定了 15 种简单烷烃的气相酸度，其中烷基三甲基硅烷与氢氧根离子反应生成三甲基硅氧离子混合物。烷烃和烷基二甲基硅氧烷离子通过失去甲烷。该反应建议通过向硅烷中加入氢氧根离子以形成五配位硅酸根离子中间体，该中间体通过两种过渡态分解，一种是在甲基上带负电荷，另一种是在甲基上带负电荷。烷基。产生的硅氧根离子的比例被认为与甲基和烷基阴离子的相对碱度相关。该方法使用已知的甲烷酸度 (/Delta/H/亚酸/) = 416 进行校准。6 kcal/mol 和苯（/Delta/H/度//亚酸/ = 400.7 kcal/mol）。一般而言，发现甲基取代可稳定气相中的烷基阴离子，但发现乙基阴离子比甲基阴离子碱性更强。通过将气相酸度与键解离能结合起来，可以计算出相应烷基的电子亲和力 (EA)。发现许多更简单的烷基自由基具有负的 EA。给出了所研究烷基的结果。«
• Determination of the gas-phase acidities of halogen-substituted aromatic compounds using the silane-cleavage method
  作者：Paul G. Wenthold、Robert R. Squires

  DOI：10.1002/jms.1190300105

  日期：1995.1

  The gas-phase acidities of halogen-substituted aromatic compounds have been determined in a flowing afterglowtriple quadrupole apparatus with use of the silane cleavage method developed by DePuy and co-workers [C. H. DePuy, S. Gronert, S. E. Barlow, V. M. Bierbaum and R. Damrauer, J. Am. Chem. Soc., 111, 1968 (1989)]. In this method the relative yields of siloxide ion products produced in reactions of OH− with trimethylsilyl- or phenyldimethylsilyl-substituted aromatic compounds are correlated with the difference in gas-phase acidity of the accompanying neutral products. Acidities are reported for different ring-positions in fluoro-, chloro- and bromobenzene, chloro- and bromonaphthalene and benzyl chloride. Excellent precision is achieved in most cases, with assigned uncertainties less than 2–3 kcal/mol. Good agreement is obtained between the acidities determined with use of two different types of silane precursor. Halogen-substitution increases the gas-phase acidities of benzene and naphthalene by similar amounts (13–14 kcal/mol). The effects on different ring-positions in benzene and naphthalene are shown to be primarily inductive in nature, falling-off by a consistent 2.5–3.5 kcal/mol per bond separating the acidic site from the halogen-bearing carbon in the chlorine and bromine-substituted systems. Larger effects are evident in the positional acidities of fluorobenzene. The meta and para position acidities of halobenzenes are shown to be linearly correlated with the acidities of the corresponding meta and para halophenols, haloanilines and halotoluenes.

  卤素取代的芳香化合物的气相酸性通过使用DePuy及其合作者开发的硅烷裂解法在流动后辉三重四极杆仪器中进行了测定[C. H. DePuy, S. Gronert, S. E. Barlow, V. M. Bierbaum和R. Damrauer, J. Am. Chem. Soc., 111, 1968 (1989)]。在该方法中，与OH−与三甲基硅基或苯基二甲基硅基取代芳香化合物反应所生成的硅氧负离子产物的相对产率与伴随的中性产物的气相酸性差异相关联。不同环位的氟、氯和溴苯、氯和溴萘以及苄氯的酸性结果已被报告。在大多数情况下实现了优异的精确度，赋值不确定性低于2-3 kcal/mol。使用两种不同类型的硅烷前体测定的酸性结果之间获得良好的一致性。卤素取代使苯和萘的气相酸性均增加了相似的值（13-14 kcal/mol）。氯和溴取代体系中，苯和萘中不同环位的影响主要是感应效应，酸性位点与含卤碳原子之间每隔一个键的酸性降低幅度一致为2.5-3.5 kcal/mol。在氟苯的位置酸性中，明显表现出更大的影响。卤苯的对位和间位酸性与相应的间位和对位卤酚、卤代苯胺和卤代甲苯的酸性呈线性相关。
• O'Hair, Richard A.J.; Sheldon, John C.; Bowie, John H., Australian Journal of Chemistry, 1989, vol. 42, # 4, p. 489 - 496
  作者：O'Hair, Richard A.J.、Sheldon, John C.、Bowie, John H.、Damrauer, Robert、DePuy, Charles H.

  DOI：——

  日期：——