1,4-bis(trimethylsilyl)-2-butyne | 21752-78-3

• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 英文名称: 1,4-bis(trimethylsilyl)-2-butyne
• 英文别名: 1,4-bis(trimethylsilylmethyl)acetylene；1,4-bis(trimethylsilyl)but-2-yne；1.4-Bis-(trimethylsilyl)-butin-(2)；trimethyl(4-trimethylsilylbut-2-ynyl)silane
• CAS: 21752-78-3
• 化学式: C₁₀H₂₂Si₂
• 分子量: 198.456
• InChiKey: UPAAZWVMKHGLNU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.67
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  1,4-bis(trimethylsilyl)-2-butyne 在 氢氧化钾 、 乙基锂 作用下， 以 1,4-二氧六环 、 乙醚 为溶剂， 反应 22.0h， 生成 (3,6-Bis-trimethylsilanyl-hex-4-ynyl)-isopropyl-amine
  参考文献：
  名称：

  Synthèse et protodésilylation de silanes α-alléniques hétérocycliques

  摘要：

  Some psi-functional propargylic-bis-trimethylsilanes, easily prepared from propargyltrimethylsilane through classical methods, allow a convenient one-pot synthesis of 2-alkyl-4-trimethylsilyl-3-vinylidenetetrahydropyranes and N-alkyl-4-trimethylsilyl-3-vinylidene-piperidines. These new silanes undergo a protodesilylation reaction leading to conjugated heterocyclic dienes.

  DOI：

  10.1016/0022-328x(94)85029-1
• 作为产物：
  描述：

  碘甲基三甲基硅烷 、 炔丙基三甲基硅烷 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 以60%的产率得到1,4-bis(trimethylsilyl)-2-butyne
  参考文献：
  名称：

  迁移1,2,3,3,3,5-三烷基甲硅烷基或乙烯基阳离子：双（三（甲基）硅基甲硅烷基）-1,4 alcynes-2合成的二乙炔（synthèsedediènesconjuguéssilylés）

  摘要：

  烷基α-取代的1,4-双（三甲基甲硅烷基）-2-炔烃与亲电试剂反应生成甲硅烷基化的共轭二烯，这是由于三甲基甲硅烷基向乙烯基阳离子中心的1,2-转移。

  DOI：

  10.1016/0022-328x(88)80021-4
• 作为试剂：
  描述：

  乙酰化葡萄烯糖 、 D-三乙酰半乳糖烯 在 1,4-bis(trimethylsilyl)-2-butyne 、 四氯化锡 作用下， 以 二氯甲烷 为溶剂， 以53%的产率得到Acetic acid (2R,3R,6S)-6-[2-((2S,5S,6R)-5-acetoxy-6-acetoxymethyl-5,6-dihydro-2H-pyran-2-yl)-1-methylene-allyl]-2-acetoxymethyl-3,6-dihydro-2H-pyran-3-yl ester
  参考文献：
  名称：

  Synthesis of Silylallene Glycosides and Diene Diglycosides by C-Glycosidation of d-Glucal with 1,4-Bis(trimethylsilyl)-2-butyne

  摘要：

  Silylmethylallenyl glycosides, symmetrical and unsymmetrical diene glycosides, were synthesized by C-glycosidation with 1,4-bis(trimethylsilyl)2-butyne in good yield. The nature of the product is controlled by the choice of Lewis acid, (BF3OEt2)-O-., or SnCl4. The efficient construction of unsymmetrical diene glycosides was achieved in one pot on the basis of the order of addition of sugar starting materials.

  DOI：

  10.1021/ol050265o

文献信息

• A Strategy for C−H Activation of Pyridines:  Direct C-2 Selective Alkenylation of Pyridines by Nickel/Lewis Acid Catalysis
  作者：Yoshiaki Nakao、Kyalo Stephen Kanyiva、Tamejiro Hiyama

  DOI：10.1021/ja710766j

  日期：2008.2.1

  The C-2 selective alkenylation of pyridine derivatives is achieved with a catalyst consisting of nickel and Lewis acid. Use of diorganozinc compounds as the Lewis acid catalyst gives C-2 monoalkenylation products, whereas AlMe3 changes the reaction course to afford C-2 dienylated products, which are derived from double insertion of alkynes into the C(2)−H bond. The reaction demonstrates a broad substrate

  吡啶衍生物的 C-2 选择性烯基化是通过由镍和路易斯酸组成的催化剂实现的。使用二有机锌化合物作为路易斯酸催化剂产生 C-2 单烯基化产物，而 AlMe3 改变反应过程以提供 C-2 二烯基化产物，其源自炔烃双插入 C(2)-H 键。与之前吡啶直接 CH 官能化的例子相比，该反应展示了广泛的底物范围，并在温和条件下以高化学选择性、区域选择性和立体选择性进行。
• Formation and ring-opening of 8-oxabicyclo[3.2.1]oct-6-en-3-ones from (4+3)-cycloaddition of furan and chlorocyclopentanone derivatives
  作者：Xuefeng Gao、Michael Harmata

  DOI：10.1016/j.tet.2013.05.051

  日期：2013.9

  During the course of studying an ene reaction of an oxyallylic cation derived from a 2-chlorocyclopentanone system, the reactive species was found to undergo quite facile (4+3)-cycloadditions with furans. Moreover, the (4+3)-cycloadducts derived from furans were prone to ring-opening, which resulted in the formation of 2-furanyl cyclopentanones in excellent yields. An acid-catalyzed mechanism was proposed

  在研究衍生自2-氯环戊酮体系的羟基烯丙基阳离子的烯反应过程中，发现反应性物种与呋喃的反应非常容易（4 + 3）-环加成。此外，源自呋喃的（4 + 3）-环加合物易于开环，这导致以优异的产率形成2-呋喃基环戊烷酮。提出了一种酸催化机制用于开环过程。确定了两个反应的几个例子。
• DTBB-Catalysed lithiation of 1,4-dichloro-2-butyne under Barbier conditions: Synthesis of functionalised alkynes
  作者：Albert Guijarro、Miguel Yus

  DOI：10.1016/0040-4020(94)00936-o

  日期：1995.1

  The reaction of 1,2-dichloro-2-butyne (1) with an excess of lithium powder and a catalytic amount of 4,4′-di-tert-butylbiphenyl (DTBB, 2.5 mol %) in the presence of an electrophile [Me3SiCl, ButCHO, Me2CO, Et2CO, (CH2)4CO, (CH2)5CO, (CH2)7CO] in THF at −40°C leads, after hydrolysis with water, to the corresponding disubstituted acetylenes 2 in moderate yields.

  1,2-二氯-2-丁炔（1）与过量的锂粉末和4,4催化量的反应' -二-叔-butylbiphenyl（DTBB，2.5摩尔％）在亲电的存在[我3的SiCl，卜吨CHO中，Me 2 CO，等2 CO，（CH 2）4 CO，（CH 2）5 CO，（CH 2）7 CO]在THF中在-40°C的引线，用水水解后，以中等收率得到相应的二取代的乙炔2。
• Nickel/Lewis Acid-Catalyzed Carbocyanation of Alkynes Using Acetonitrile and Substituted Acetonitriles
  作者：Akira Yada、Tomoya Yukawa、Hiroaki Idei、Yoshiaki Nakao、Tamejiro Hiyama

  DOI：10.1246/bcsj.20100023

  日期：2010.6.15

  Nickel/Lewis acid dual catalysis is found to effect the carbocyanation reaction of alkynes using acetonitrile and substituted acetonitriles to give a range of variously substituted acrylonitriles. The addition of propionitrile across alkynes is also demonstrated briefly to give the corresponding ethylcyanation products in good yields, whereas the reaction of butyronitrile gives significant amounts of hydrocyanation products due possibly to β-hydride elimination of a propylnickel intermediate. The reaction of optically active α-phenylpropionitrile suggests a reaction mechanism that involves oxidative addition of a C–CN bond with retention of its absolute configuration.

  镍/路易斯酸双催化体系被发现能够有效地促进乙腈和取代乙腈与炔烃的碳氰化反应，生成一系列不同取代的丙烯腈。简要展示的丙腈与炔烃的加成反应也能高效地得到相应的乙基氰化产物，而丁腈参与的反应则因可能的丙基镍中间体β-氢消除作用而得到显著量的氢氰化产物。光学活性α-苯基丙腈的反应表明其反应机制涉及C–CN键的氧化加成，并保留其绝对构型。
• d-Orbital effects in silicon substituted π-electron systems. Part XII. Some spectroscopic properties of alkyl and silyl acetylenes and polyacetylenes
  作者：H. Bock、H. Seidl

  DOI：10.1039/j29680001158

  日期：——

  signals, and electronic transitions are reported for acetylenes X·[CC]n·X (n= 1, 2, 3; X = H, CMe3, CH2·SiMe3, SiMe3). Comparison with the corresponding data of ethylene and butadiene derivatives indicates stronger electron back-donation to silicone Si â†� Cπ which is interpreted as being due to interactions with both of the perpendicular acetylene π-components. The inductive polarization +l(SiR3) >

  报告了乙炔X·[ CC] n ·X（n = 1，2，3; X = H，CMe 3，CH 2 ·SiMe 3的垂直电离能，特征振动频率，1 H nmr信号和电子跃迁，SiMe 3）。与乙烯和丁二烯衍生物的相应数据比较指示更强的电子背捐赠硅氧烷的Si â† Ç π这被解释为是由于与两者的垂直乙炔相互作用π -components。感应极化+ l（SiR 3）> + /（CR 3）可由CH 2 ·SiR 3基团的取代作用来估计。