(Z)-3-[tris(trimethylsilyl)silyl]propenoic acid | 838852-54-3

• 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: (Z)-3-[tris(trimethylsilyl)silyl]propenoic acid
• 英文别名: 3-[tris(trimethylsilyl)silyl]propenoic acid；(Z)-3-tris(trimethylsilyl)silylprop-2-enoic acid
• CAS: 838852-54-3
• 化学式: C₁₂H₃₀O₂Si₄
• 分子量: 318.711
• InChiKey: NYHGVIJHDPLIFE-KHPPLWFESA-N

物化性质

• 熔点：
  82-84 °C
• 沸点：
  305.3±44.0 °C(Predicted)
• 密度：
  0.890±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.87
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4-(三氟甲基)苄醇 、 (Z)-3-[tris(trimethylsilyl)silyl]propenoic acid 在 4-二甲氨基吡啶 、 盐酸-N-乙基-Nˊ-(3-二甲氨基丙基)碳二亚胺 作用下， 以 二氯甲烷 为溶剂， 反应 20.0h， 以78%的产率得到(Z)-4-(trifluoromethyl)benzyl 3-[tris(trimethylsilyl)silyl]propenoate
  参考文献：
  名称：

  Modification and chemical transformation of Si(111) surface

  摘要：

  Modification of hydrogen-terminated Si(111) surfaces by hydrosilylation of activated alkenes and further chemical transformation of the modified surfaces is reported. A Si(111)-H surface was reacted with activated alkenes such as acrylate esters, acrylonitrile, and maleic anhydride under mild conditions to give modified surfaces with terminal functional groups. A modified surface with a terminal ester group was reduced by LiAlH4 to give a hydroxy-terminated surface, and the hydroxy-terminated surface was transformed to a bromo-terminated surface. XPS analysis revealed that the brominated surface ( Si(111)-CH2CH2CH2Br) had 32% coverage with the 3-bromopropyl group. Ester and amide formation reactions were carried out on hydroxy- and carboxy-terminated Si surfaces by reaction with tert-butoxycarbonyl glycine, glycine tort-butyl ester, 2,2,2-trifluoroethanol and 4-trifluoromethylbenzyl alcohol in the presence of carbodiimide. XPS characterization indicated that the esters and amide were successfully formed with coverage ranging from 16% to 58%. Coverage ratios of octadecyl ester modified surfaces were also estimated by combination of surface reduction and gas chromatography analysis to be 25-35%. (c) 2006 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2006.09.048
• 作为产物：
  描述：

  三(三甲基硅基)硅烷 、 丙炔酸 在 氧气 作用下， 以 水 为溶剂， 反应 24.0h， 以99%的产率得到(Z)-3-[tris(trimethylsilyl)silyl]propenoic acid
  参考文献：
  名称：

  水中多个键的氢化硅烷化反应的不同自由基引发技术：双氧引发

  摘要：

  自由基引发方法与带有CC多重键的有机化合物的经典氢化硅烷化反应的相关性是由于需要考虑到其在表面化学上的应用，需要提出更新和更有效的方法来实现此反应。过去，当使用有机溶剂时，已记录了用于链引发反应的热和光化学方法（偶氮化合物的热和光化学分解）。我们在此介绍了CC三键与三（三甲基甲硅烷基）硅烷（（Me 3 Si）3SiH）在水中。在没有硅烷的化学自由基前体的情况下，该引发技术面临光化学自由基引发，并且还面临由偶氮化合物分解引发的经典热引发，二者均在水中进行。在水中研究的基于自由基的双氧引发方法显示出氢化硅烷化烯烃的最高Z：E立体选择性比。版权所有©2010 John Wiley＆Sons，Ltd.

  DOI：

  10.1002/poc.1703

文献信息

• Regioselective Hydrosilylations of Propiolate Esters with Tris(trimethylsilyl)silane
  作者：Yang Liu、Shoko Yamazaki、Shinichi Yamabe

  DOI：10.1021/jo048371b

  日期：2005.1.1

  Lewis acid and substituent dependency on the regioselectivity of hydrosilylation of propiolate esters 1a−c with tris(trimethylsilyl)silane (2a) was found. The reaction of methyl and ethyl propiolate esters and 2a without Lewis acid and in the presence of EtAlCl2 and Et2AlCl gave β-silicon-substituted Z-alkenes 3 selectively. On the other hand, reaction in the presence of AlCl3 in dichloromethane gave

  发现路易斯酸和取代基对丙酸酯酸酯1a - c与三（三甲基甲硅烷基）硅烷（2a）的硅氢化反应的区域选择性的依赖性。在没有路易斯酸的情况下，在EtAlCl 2和Et 2 AlCl的存在下，丙酸甲酯和丙酸乙酯与2a的反应选择性地产生了β-硅取代的Z-烯烃3。另一方面，在二氯甲烷中存在AlCl 3的情况下反应，得到α-硅取代的烯烃4。如果是三氟乙基丙酸酯1c与氯化铝基路易斯酸反应，仅得到α-硅取代的烯烃4。提出了两种竞争机制，自由基和离子竞争机制，作为这些反应中显示的互补区域选择性的来源。通过计算获得自由基形成步骤的过渡状态。在室温下，在没有路易斯酸和没有溶剂的情况下，各种反应性乙炔底物和2a的反应选择性地产生了β-硅取代的Z-烯烃3。
• Radical Reactions in Aqueous Medium Using (Me₃Si)₃SiH
  作者：Al Postigo、Sergey Kopsov、Carla Ferreri、Chryssostomos Chatgilialoglu

  DOI：10.1021/ol7020803

  日期：2007.12.1

  (Me3Si)(3)SiH was used as a successful reagent in a variety of radical-based transformations in water. The system comprising substrate, silane, and initiator (ACCN) mixed in aqueous medium at 100 degrees C worked well for both hydrophilic and hydrophobic substrates, with the only variation that an amphiphilic thiol was also needed in case of the water-soluble compounds.
• Modification and chemical transformation of Si(111) surface
  作者：Yang Liu、Shoko Yamazaki、Suguru Izuhara

  DOI：10.1016/j.jorganchem.2006.09.048

  日期：2006.12

  Modification of hydrogen-terminated Si(111) surfaces by hydrosilylation of activated alkenes and further chemical transformation of the modified surfaces is reported. A Si(111)-H surface was reacted with activated alkenes such as acrylate esters, acrylonitrile, and maleic anhydride under mild conditions to give modified surfaces with terminal functional groups. A modified surface with a terminal ester group was reduced by LiAlH4 to give a hydroxy-terminated surface, and the hydroxy-terminated surface was transformed to a bromo-terminated surface. XPS analysis revealed that the brominated surface ( Si(111)-CH2CH2CH2Br) had 32% coverage with the 3-bromopropyl group. Ester and amide formation reactions were carried out on hydroxy- and carboxy-terminated Si surfaces by reaction with tert-butoxycarbonyl glycine, glycine tort-butyl ester, 2,2,2-trifluoroethanol and 4-trifluoromethylbenzyl alcohol in the presence of carbodiimide. XPS characterization indicated that the esters and amide were successfully formed with coverage ranging from 16% to 58%. Coverage ratios of octadecyl ester modified surfaces were also estimated by combination of surface reduction and gas chromatography analysis to be 25-35%. (c) 2006 Elsevier B.V. All rights reserved.
• Different radical initiation techniques of hydrosilylation reactions of multiple bonds in water: dioxygen initiation
  作者：Al Postigo、Norma Sbarbati Nudelman

  DOI：10.1002/poc.1703

  日期：——

  reactions of organic compounds bearing CC multiple bonds is due to the need to come up with newer and more effcient methods to effect this reaction, on account of its applications on surface chemistry. In the past, when organic solvents were employed, thermal and photochemical methods for the chain initiation reaction have been documented (thermal and photochemical decomposition of azo compounds). We

  自由基引发方法与带有CC多重键的有机化合物的经典氢化硅烷化反应的相关性是由于需要考虑到其在表面化学上的应用，需要提出更新和更有效的方法来实现此反应。过去，当使用有机溶剂时，已记录了用于链引发反应的热和光化学方法（偶氮化合物的热和光化学分解）。我们在此介绍了CC三键与三（三甲基甲硅烷基）硅烷（（Me 3 Si）3SiH）在水中。在没有硅烷的化学自由基前体的情况下，该引发技术面临光化学自由基引发，并且还面临由偶氮化合物分解引发的经典热引发，二者均在水中进行。在水中研究的基于自由基的双氧引发方法显示出氢化硅烷化烯烃的最高Z：E立体选择性比。版权所有©2010 John Wiley＆Sons，Ltd.