3-propionitrile | 131379-56-1

• 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: 3-propionitrile
• 英文别名: 3-Tris(trimethylsilyl)silylpropanenitrile
• CAS: 131379-56-1
• 化学式: C₁₂H₃₁NSi₄
• 分子量: 301.727
• InChiKey: JEJKXWMQSRPJHF-UHFFFAOYSA-N

物化性质

• 熔点：
  100 °C (sublm)(Press: 0.08 Torr)
• 沸点：
  295.9±42.0 °C(Predicted)
• 密度：
  0.831±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  23.8
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  3-propionitrile 在 2,3-二甲基-1,4-苯醌 、 四丁基氟化铵 、 氧气 作用下， 以 四氢呋喃 为溶剂， 反应 0.83h， 以71%的产率得到3-羟基丙腈
  参考文献：
  名称：

  Tris(trimethylsilyl)silane: an efficient hydrosilylating agent of alkenes and alkynes

  摘要：

  Tris(trimethylsilyl)silane adds across the double bond of a variety of mono-, di-, and trisubstituted olefins under free-radical conditions in good yields. The reaction, which proceeds via a free-radical chain mechanism, is highly regioselective (anti-Markovnikov). Addition to prochiral olefins bearing an ester group is highly stereoselective. The factors that control the stereochemistry have been discussed terms of preferred conformations of the intermediate carbon-centered radicals and are thought to be of steric origin.

  DOI：

  10.1021/jo00040a048
• 作为产物：
  描述：

  三(三甲基硅基)硅烷 、 丙烯腈 在 四氢吡喃 、 偶氮二异庚腈 作用下， 反应 4.0h， 以86%的产率得到3-propionitrile
  参考文献：
  名称：

  使用THP作为溶剂的自由基链反应

  摘要：

  与THF相比，已发现THP（四氢吡喃）对自氧化具有极好的稳定性。当在THF中作为溶剂进行氢化三丁基锡介导的自由基环化时，会遭受从溶剂中夺取氢的竞争，而使用THP导致该过程的程度可忽略不计。使用THP作为溶剂，成功进行了氢化三丁基锡，TTMSS和己硫醇介导的自由基反应。

  DOI：

  10.1016/j.tetlet.2007.11.039

文献信息

• Alkyl isocyanides as precursors for the formation of carbon-carbon bonds
  作者：C. Chatgilialoglu、B. Giese、B. Kopping

  DOI：10.1016/s0040-4039(00)98016-x

  日期：1990.1

  Tris(trimethylsilyl)silane is an effective mediator for the formation of carbon-carbon bonds via radicals using alkyl isocyanides as precursors.

  三（三甲基甲硅烷基）硅烷是通过使用烷基异氰化物作为前体的自由基形成碳-碳键的有效介体。
• Evaluation of cyclopentyl methyl ether (CPME) as a solvent for radical reactions
  作者：Shoji Kobayashi、Hiroyuki Kuroda、Yuta Ohtsuka、Takashi Kashihara、Araki Masuyama、Kiyoshi Watanabe

  DOI：10.1016/j.tet.2013.01.030

  日期：2013.3

  explored the potential of cyclopentyl methyl ether (CPME) as a solvent for radical reactions. Hydrostannation, hydrosilylation, hydrothiolation, and tributyltin hydride mediated reductions were successfully carried out in CPME. GC–MS analysis indicated that CPME degraded into methyl pentanoate, cyclopentanone, 2-cyclopenten-1-ol, and cyclopentanol under thermal radical conditions, albeit only slightly.

  我们已经探索了环戊基甲基醚（CPME）作为自由基反应溶剂的潜力。在CPME中成功进行了氢化锡氢化，氢化硅烷化，氢化硫氢化和三丁基氢化锡介导的还原反应。GC-MS分析表明，CPME在热自由基条件下降解为戊酸甲酯，环戊酮，2-环戊烯-1-醇和环戊醇，尽管仅有少量。我们还通过CPME实现了含自由基的一锅反应，以证明其适用于多步反应。
• Tris(trimethylsilyl)silyl versus tris(trimethylsilyl)germyl: Radical reactivity and oxidation ability
  作者：Jacques Lalevée、Nicolas Blanchard、Bernadette Graff、Xavier Allonas、Jean Pierre Fouassier

  DOI：10.1016/j.jorganchem.2008.08.039

  日期：2008.11

  (TMS)3SiH toward the t-butoxyl, the t-butylperoxyl and the phosphinoyl radicals. A similar behavior is noted for an aromatic ketone triplet state. II exhibits a lower absolute electronegativity: accordingly, the addition to electron rich alkenes is less efficient than for I. Radical II is also found less reactive for both the peroxylation (II+O2→II-O2) and the halogen abstraction reactions. The rearrangement

  提供了三（三甲基甲硅烷基）甲硅烷基I和三（三甲基甲硅烷基）甲锗烷基II自由基反应性的比较。通过激光闪光光解，量子力学计算和电子自旋共振（ESR）实验检查了它们的形成以及在多种化学过程（双键加成，卤素抽象，过氧自由基形成等）中遇到的反应性。起始化合物（TMS）3 GeH比（TMS）3 SiH对叔丁氧基，叔丁基过氧基和膦酰基具有更高的反应性。对于芳族酮三重态也观察到类似的行为。II表现出较低的绝对电负性：因此，向富电子的烯烃中添加的效率低于I的效率。还发现自由基II对于过氧化（II + O2→II-O2）和卤素提取反应均具有较低的反应性。II-O2的重排比I-O2的重排慢；这与过程各自的放热有关。
• Charge Separation in Metal‐Organic Framework Enables Heterogeneous Thiol Catalysis
  作者：Shengxian Cheng、Jing Ouyang、Muqing Li、Yingxue Diao、Jiachen Yao、Fengxing Li、Yat‐For Lee、Herman Ho‐Yung SUNG、Ian Williams、Zhengtao Xu、Yangjian Quan

  DOI：10.1002/anie.202300993

  日期：2023.6.19

  Photoinduced metal–organic framework (MOF) enabled heterogeneous thiol catalysis has been achieved for the first time. MOF Zr‐TPDCS‐1, consisting of Zr₆‐clusters and TPDCS linkers (TPDCS=3,3′′,5,5′′‐tetramercapto[1,1′:4′,1′′‐terphenyl]‐4,4′′‐dicarboxylate), effectively catalyzed the borylation, silylation, phosphorylation, and thiolation of organic molecules. Upon irradiation, the fast electron transfer from TPDCS to Zr₆‐cluster is believed to facilitate the formation of the thiyl radical, a hydrogen atom transfer catalyst, which competently abstracts the hydrogen from borane, silane, phosphine, or thiol for generating the corresponding element radical to engender the chemical transformations. The elaborate control experiments evidenced the generation of thiyl radicals in MOF and illustrated a radical reaction pathway. The gram‐scale reaction worked well, and the product was conveniently separated via centrifugation and vacuum with a turnover number (TON) of ≈3880, highlighting the practical application potential of heterogeneous thiyl‐radical catalysis.

  摘要 首次实现了光诱导金属有机框架（MOF）异相硫醇催化。由 Zr6 簇和 TPDCS 连接器（TPDCS=3,3′′,5,5′′-四巯基[1,1′：4′,1′′-三联苯]-4,4′′-二甲酸酯），可有效催化有机分子的硼酸化、硅化、磷酸化和硫代化。在辐照下，TPDCS 与 Zr6 簇之间的快速电子转移被认为促进了硫基的形成，硫基是一种氢原子转移催化剂，能从硼烷、硅烷、膦或硫醇中抽取氢，生成相应的元素自由基，从而引发化学转化。精心设计的对照实验证明了硫基自由基在 MOF 中的生成，并说明了自由基反应途径。克级反应效果良好，产物经离心和真空分离后，周转次数（TON）≈3880，凸显了异相硫基自由基催化的实际应用潜力。
• Tris(trimethylsilyl)silane as a radical-based reducing agent in synthesis
  作者：M. Ballestri、C. Chatgilialoglu、K. B. Clark、D. Griller、B. Giese、B. Kopping

  DOI：10.1021/jo00002a035

  日期：1991.1

  Tris(trimethylsilyl)silane is an effective reducing agent for organic halides, selenides, xanthates, and isocyanides, as well as an effective hydrosilylating agent for dialkyl ketones and alkenes. The silane functions as a mediator in the formation of intermolecular carbon-carbon bonds via radicals and allows a variety of organic substrates to be used as alkyl radical percursors. Absolute rate constants for the reaction of (Me3Si)3Si radicals with a variety of organic compounds have been measured in solution by laser flash photolysis. At 294 K rate constants are > 5 x 10(7) M-1 s-1 for C = C double bonds that are activated by neighboring pi-electron systems or by electron-withdrawing groups. For other substrates, reactivities decreased in the order xanthate > selenide > isocyanide > nitro > sulfide.