3-iodo-5-[(trimethylsilanyl)ethynyl]benzoic acid methyl ester | 247234-88-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 3-iodo-5-[(trimethylsilanyl)ethynyl]benzoic acid methyl ester
• 英文别名: Methyl 3-iodo-5-[2-(trimethylsilyl)ethynyl]benzoate；methyl 3-iodo-5-(2-trimethylsilylethynyl)benzoate
• CAS: 247234-88-4
• 化学式: C₁₃H₁₅IO₂Si
• 分子量: 358.251
• InChiKey: IOQMDVZBPRWULE-UHFFFAOYSA-N

物化性质

• 沸点：
  363.6±42.0 °C(Predicted)
• 密度：
  1.45±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.31
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3-iodo-5-[(trimethylsilanyl)ethynyl]benzoic acid methyl ester 在 copper(l) iodide 、 Pb(dba)2 、 三乙胺 、 三苯基膦 、 碘甲烷 作用下， 反应 48.0h， 生成 3-[3-(3-tert-Butyl-5-{3-[3-tert-butyl-5-(3-iodo-phenylethynyl)-phenylethynyl]-phenylethynyl}-phenylethynyl)-phenylethynyl]-5-trimethylsilanylethynyl-benzoic acid methyl ester
  参考文献：
  名称：

  Geometrically-Controlled and Site-Specifically-Functionalized Phenylacetylene Macrocycles

  摘要：

  A convergent, stepwise synthesis of linear phenylacetylene sequences (PASs) is described. The methodology allows for complete control over chain length, sequence order of monomers, and functional group placement. Chain growth follows geometric progression thus allowing sequences of length 2(n), where n is the number of repetitive cycles, to be assembled in a total of just 3.n steps (two deprotections and one coupling for each cycle). Sequences of length other than 2(n) as well as sequences having a particular arrangement of co-monomer units, can also be realized by merging parallel repetitive cycles. Upon deprotection of the termini, these PASs can be cyclized to phenylacetylene macrocycles (PAMs) in high yield. Control over the ring structure of PAMs is determined by the chemistry of precursor PASs; the size of the macrocycle is related to the sequence length, while the geometry of the macrocycle and the position of the pendant functional groups on the macrocycle is governed by co-monomer sequence order. PAMs with four, five, six, seven, and twelve phenylacetylene monomer units, as well as a variety of site-specifically-functionalized PAMs, have been synthesized with this method. Finally, functional group transformations have been performed on some of the PAMs which lead to PAMs with new functionality. The versatile and efficient approach to this family of geometrically well-defined macrocycles offers potential for producing st set of modular building blocks to rationally assemble molecular crystals and liquid crystals. For this reason, the solid-state characteristics of the hydrocarbon skeletons are of interest. In spite of their solubility in common solvents, hydrocarbon PAMs are shown to yield crystals with remarkable thermal stability and high melting points. Three PAM hydrocarbons are shown not to exhibit melting transitions up to ca 400 degrees C, at which point an abrupt thermal irreversible reaction occurs, apparently involving a solid-state polymerization of the acetylene units.

  DOI：

  10.1021/ja00089a012
• 作为产物：
  描述：

  在 碘甲烷 作用下， 反应 12.0h， 生成 3-iodo-5-[(trimethylsilanyl)ethynyl]benzoic acid methyl ester
  参考文献：
  名称：

  Geometrically-Controlled and Site-Specifically-Functionalized Phenylacetylene Macrocycles

  摘要：

  A convergent, stepwise synthesis of linear phenylacetylene sequences (PASs) is described. The methodology allows for complete control over chain length, sequence order of monomers, and functional group placement. Chain growth follows geometric progression thus allowing sequences of length 2(n), where n is the number of repetitive cycles, to be assembled in a total of just 3.n steps (two deprotections and one coupling for each cycle). Sequences of length other than 2(n) as well as sequences having a particular arrangement of co-monomer units, can also be realized by merging parallel repetitive cycles. Upon deprotection of the termini, these PASs can be cyclized to phenylacetylene macrocycles (PAMs) in high yield. Control over the ring structure of PAMs is determined by the chemistry of precursor PASs; the size of the macrocycle is related to the sequence length, while the geometry of the macrocycle and the position of the pendant functional groups on the macrocycle is governed by co-monomer sequence order. PAMs with four, five, six, seven, and twelve phenylacetylene monomer units, as well as a variety of site-specifically-functionalized PAMs, have been synthesized with this method. Finally, functional group transformations have been performed on some of the PAMs which lead to PAMs with new functionality. The versatile and efficient approach to this family of geometrically well-defined macrocycles offers potential for producing st set of modular building blocks to rationally assemble molecular crystals and liquid crystals. For this reason, the solid-state characteristics of the hydrocarbon skeletons are of interest. In spite of their solubility in common solvents, hydrocarbon PAMs are shown to yield crystals with remarkable thermal stability and high melting points. Three PAM hydrocarbons are shown not to exhibit melting transitions up to ca 400 degrees C, at which point an abrupt thermal irreversible reaction occurs, apparently involving a solid-state polymerization of the acetylene units.

  DOI：

  10.1021/ja00089a012

文献信息

• Synthesis of Well-Defined Tower-Shaped 1,3,5-Trisubstituted Adamantanes Incorporating a Macrocyclic Trilactam Ring System
  作者：Quan Li、Changshu Jin、Pavel A. Petukhov、Aleksey V. Rukavishnikov、Tatiana O. Zaikova、Avinash Phadke、Donald H. LaMunyon、Melissa D. Lee、John F. W. Keana

  DOI：10.1021/jo035640+

  日期：2004.2.1

  We describe the synthesis of two novel well-defined tower-shaped 1,3,5-trisubstituted adamantanes 30 and 33 that incorporate a macrocyclic trilactam ring system. Each nanoscale molecule has a broad tripodal base consisting of three identical sulfur-containing termini as the tripod feet, 4-acetylsulfanylmethylphenyl units in the case of 30 and 3,5-bis(acetylsulfanylmethyl)phenyl units in the case of

  我们描述了两个新的明确定义的塔形的1,3,5-三取代的金刚烷30和33的合成，其中结合了大环内酰胺环系统。每个纳米级分子都有一个由三个相同的含硫末端作为三脚架底脚组成的宽脚架基座，在30情况下为4-乙酰基硫烷基甲基苯基单元，在33情况下为3,5-双（乙酰基硫烷基甲基）苯基单元。硫原子被设计为通过形成三个S-Au键将分子三价键合至镀金商品AFM尖端的顶点。刚性金刚烷衍生的头部单元在顶部具有单个氢原子，旨在扫描样品。分子30和33通过一系列涉及末端炔烃和碘代芳基的Sonogashira偶联反应，由1,3,5-三乙炔基金刚烷酰胺合成。大环三内酰胺单元被包括在内以增加刚度。我们证明了分子30足够大且坚固，可以通过常规AFM尖端进行可视化。这些纳米级分子也可以作为化学上明确定义的纳米级对象用于AFM尖端的校准。
• Hollow Sphere Formation from a Three-Dimensional Structure Composed of an Adamantane-Based Cage
  作者：Masahide Tominaga、Kazuaki Ohara、Kentaro Yamaguchi、Isao Azumaya

  DOI：10.1021/jo500989c

  日期：2014.7.18

  An adamantane-based cage with a three-dimensional (3D) framework was synthesized by the copper-mediated acetylene coupling reaction, in which two 1,3,5-triethynyladamantane units were linked by phenyldiacetylenic bridges possessing ester groups. X-ray crystallography revealed that the cage has an internal space and accommodates a solvent molecule, which afforded molecular networks through CH/O interactions between cage molecules. Furthermore, the cage containing six ester groups spontaneously self-assembled into hollow spherical aggregates with an average diameter of 230 nm in a mixed solvent.
• A tower-shaped prototypic molecule designed as an atomically sharp tip for AFM applications
  作者：Aleksey V. Rukavishnikov、Avinash Phadke、Melissa D. Lee、Donald H. LaMunyon、Pavel A. Petukhov、John F.W. Keana

  DOI：10.1016/s0040-4039(99)01207-1

  日期：1999.8

  The synthesis of macrocycle 1 using a series of Sonogashira coupling reactions is described. This tower-shaped prototypic molecule tapers to a single hydrogen atom and is designed to serve as an atomically sharp molecular tip for atomic force microscopy imaging studies. (C) 1999 Elsevier Science Ltd. All rights reserved.
• Synthesis of new arylcarboranes as precursors for oligomers
  作者：B Förster

  DOI：10.1016/s0022-328x(99)00277-6

  日期：1999.9.15

  Some new aryl o-carboranes have been synthesized. From methyl 3-iodo-5-(trimethylsilyl-ethynyl)-benzoate (1) or butyl 3-(3,3-diethyltriazeno)-5-ethytlyl-benzoate (2), 5-ethynyl-3-iodo-benzoates (3a, 3b) were obtained, which after the reaction with the decaborane-acetonitrile complex led to the corresponding 5-(1'-(1',2'-dicarba-closo-dodecaboranyl))-3-iodo-benzoates (4a, 4b). Furthermore, the methyl 3-iodo-5- (trimethylsilyl-ethynyl)-benzoate (1) is the starting material for the synthesis of a bis-carborane. Compound 1. is modified to the methyl 3,5-bis(trimethylsilyl-ethynyl)-benzoate (5), which is deprotected to give the methyl 3,5-bis(ethynyl)-benzoate (6). Compound 6 reacted with the decaborane-acetonitrile complex to the methyl 3,5-bis(1'-(1',2'-dicarba closo-dedecaboranyl))-benzoate (7), which wets partially degraded to the bis(tetramethylammonium)-3,5-bis(7'-(8'-dicarba-nido-undecaboranyl))methoxycarbonylphenyl (8). (C) 1999 Elsevier Science S.A. All rights reserved.