4-{2-[4-(acetylthio)phenyl]ethynyl}phenylacetylene | 412300-34-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯硫酚酯
• 英文名称: 4-{2-[4-(acetylthio)phenyl]ethynyl}phenylacetylene
• 英文别名: thioacetic acid S-[4-(4-ethynylphenylethynyl)phenyl] ester；1-acetylthio-(4-(4'-ethynyl)phenylethynyl)benzene；S-(4-((4-ethynylphenyl)ethynyl)phenyl)ethanethioate；AKF-III-85；S-[4-[2-(4-ethynylphenyl)ethynyl]phenyl] ethanethioate
• CAS: 412300-34-6
• 化学式: C₁₈H₁₂OS
• 分子量: 276.359
• InChiKey: KCPKDQVPGQYMEJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  20
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.06
• 拓扑面积：
  42.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4-{2-[4-(acetylthio)phenyl]ethynyl}phenylacetylene 在 bis-triphenylphosphine-palladium(II) chloride copper(l) iodide 、 苯甲醚 、 三乙胺 、 三氟乙酸 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 4.0h， 生成 thioacetic acid S-{4-[4-(4-sulfanylphenylethynyl)phenylethynyl]phenyl} ester
  参考文献：
  名称：

  Orthogonally Functionalized Oligomers for Controlled Self-Assembly

  摘要：

  The synthesis of molecules terminated with complementary thiol-protecting groups is described. The target compounds contain functionalities on one end known to form self-assembled monolayers on metal surfaces while at the other end an intact thioacetate is present whereby self-assembly may again occur after an in situ deprotection. Self-assembly data is reported for selected compounds to assess their efficacy in surface adhesion.

  DOI：

  10.1021/jo035821b
• 作为产物：
  描述：

  (4-溴苯基乙炔基)三甲基硅烷 在 bis-triphenylphosphine-palladium(II) chloride copper(l) iodide 、 四丁基氟化铵 、 碘 、 叔丁基锂 、 乙酸酐 、 溶剂黄146 、 三乙胺 作用下， 以 四氢呋喃 、 正戊烷 为溶剂， 反应 0.91h， 生成 4-{2-[4-(acetylthio)phenyl]ethynyl}phenylacetylene
  参考文献：
  名称：

  Orthogonally Functionalized Oligomers for Controlled Self-Assembly

  摘要：

  The synthesis of molecules terminated with complementary thiol-protecting groups is described. The target compounds contain functionalities on one end known to form self-assembled monolayers on metal surfaces while at the other end an intact thioacetate is present whereby self-assembly may again occur after an in situ deprotection. Self-assembly data is reported for selected compounds to assess their efficacy in surface adhesion.

  DOI：

  10.1021/jo035821b

文献信息

• Synthesis and Preliminary Testing of Molecular Wires and Devices
  作者：James M. Tour、Adam M. Rawlett、Masatoshi Kozaki、Yuxing Yao、Raymond C. Jagessar、Shawn M. Dirk、David W. Price、Mark A. Reed、Chong-Wu Zhou、Jia Chen、Wenyong Wang、Ian Campbell

  DOI：10.1002/1521-3765(20011203)7:23<5118::aid-chem5118>3.0.co;2-1

  日期：2001.12.3

  Presented here are several convergent synthetic routes to conjugated oligo(phenylene ethynylene)s. Some of these oligomers are free of functional groups, while others possess donor groups, acceptor groups, porphyrin interiors, and other heterocyclic interiors for various potential transmission and digital device applications. The syntheses of oligo(phenylene ethynylene)s with a variety of end groups

  本文介绍了几种共轭低聚（亚苯基乙炔基）合成路线。这些低聚物中的一些不含官能团，而其他则具有供体基团，受体基团，卟啉内部以及用于各种潜在传输和数字设备应用的其他杂环内部。提出了具有各种端基的低聚（亚苯基亚乙炔基）的合成方法，该低端基用于连接许多金属探针和表面。一些功能化分子系统表现出线性，线状，电流对电压（I（V））响应，而另一些则表现出负差分电阻（NDR）和分子随机存取记忆效应的非线性I（V）曲线。最后，描述了可以在金属电极上形成自组装单分子层的功能化低聚物的合成，从而降低了肖特基势垒。肖特基势垒研究的信息可以为分子电子学中的分子鳄鱼夹优化提供有用的见解。
• Photophysical Properties of Oligo­(phenylene ethynylene) Iridium(III) Complexes Functionalized with Metal‐Anchoring Groups
  作者：Julia Ponce、Juan Aragó、Ignacio Vayá、Jorge Gómez Magenti、Sergio Tatay、Enrique Ortí、Eugenio Coronado

  DOI：10.1002/ejic.201501409

  日期：2016.4

  The electrochemical and photophysical properties of a family of conjugated ligands and their iridium(III) cyclometallated complexes are described. They consist of a series of monocationic IrIII bis-2-phenylpyridine complexes with p-phenylethynyl-1,10-phenanthroline ligands of different length. The structure of these ligands includes terminal acetylthiol or pyridine groups, which can provide good electrical

  描述了一系列共轭配体及其铱 (III) 环金属化配合物的电化学和光物理特性。它们由一系列单阳离子 IrIII 双-2-苯基吡啶配合物与不同长度的对-苯基乙炔基-1,10-菲咯啉配体组成。这些配体的结构包括末端乙酰硫醇或吡啶基团，可以在金属电极之间提供良好的电接触。循环伏安法、吸收和发射光谱、激光闪光光解和密度泛函理论计算表明，二亚胺配体的高共轭提供了前沿轨道之间的小能隙。尽管如此，末端取代基的性质和二亚胺配体中的共轭程度对室温下的光物理特性几乎没有影响。光谱数据和理论计算同意发射激发态的电荷转移性质在室温下沿系列保持，而在刚性矩阵配体中心态也有助于低温发射。二亚胺配体的良好导电特性，这些配合物对配体的 HOMO-LUMO（HOMO = 最高占据分子轨道，LUMO = 最低未占据分子轨道）间隙的小依赖性以及发射激发态的电荷转移性质使这些复合物成为研究分子结中光电导现象的试验台。光谱数据和理论
• Synthesis and catalytic properties of p-acylthio(phenylacetylene)n substituted chiral manganese salen complexes
  作者：Morten Nielsen、Kurt V. Gothelf

  DOI：10.1039/b104103g

  日期：——

  The syntheses of three new salen ligands that are tethered to a p-acylthio(phenylacetylene)n linker are described. The two key steps in the syntheses are coupling of the p-acylthio(phenylacetylene)n linker (n = 0–2) with a 5-iodosalicylaldehyde and the subsequent condensation of the aldehyde moiety of the formed adducts with the monoimine of (S,S)-1,2-diphenylethylenediamine to give the salen ligands. In the catalytic asymmetric epoxidation reactions of (Z)-2-methylstyrene, performed using the Mn–salen complexes of these new ligands, high diastereoselectivities of up to 20 ∶ 1 and enantioselectivities of up to 89% ee are obtained. The results are compared with the analogous reaction using Jacobsen's asymmetric epoxidation catalyst and the results are very similar. The synthesised ligands are promising candidates for the immobilisation of chiral Mn–salen complexes on gold electrodes and surfaces.

  描述了与对酰硫基（苯乙炔）n 连接体相连的三种新 salen 配体的合成。合成中的两个关键步骤是对酰硫基（苯乙炔）n 连接体（n = 0–2）与 5-碘水杨醛的偶联，以及随后形成的加合物的醛部分与 (S, S)-1,2-二苯基乙二胺得到salen配体。在使用这些新配体的 Mn-salen 配合物进行 (Z)-2-甲基苯乙烯的催化不对称环氧化反应中，获得了高达 20 ∶ 1 的高非对映选择性和高达 89% ee 的对映选择性。将结果与使用Jacobsen不对称环氧化催化剂的类似反应进行比较，结果非常相似。合成的配体是有希望的候选物 将手性 Mn-salen 配合物固定在金电极和表面上。
• A spectroscopic study of self-assembled monolayer of porphyrin-functionalized oligo(phenyleneethynylene)s on gold: the influence of the anchor moiety
  作者：Somsakul Watcharinyanon、Daniel Nilsson、Ellen Moons、Andrey Shaporenko、Michael Zharnikov、Bo Albinsson、Jerker Mårtensson、Lars S. O. Johansson

  DOI：10.1039/b802914h

  日期：——

  Porphyrin-functionalized oligo(phenyleneethynylene)s (OPE) are promising molecules for molecular electronics applications. Three such molecules (1–3) with the common structure P–OPE–AG (P and AG are a porphyrin and anchor group, respectively) and different anchor groups, viz. an acetyl protected thiol, –S–COCH3 (1), an acetyl protected thiol with methylene linker, –CH2–S–COCH3 (2), and a trimethylsilylethynyl group, –CC–Si(CH3)3 (3) have been synthesized and the corresponding self-assembled monolayers (SAMs) on Au(111) substrates have been prepared. The integrity and structural properties of these films were studied by X-ray photoelectron spectroscopy and near-edge X-ray absorption fine structure spectroscopy. The results suggest that the films formed from 1 have a high orientational order with an almost upright orientation and dense packing of the molecular constituents, i.e. represent a high quality SAM. In contrast, molecule 2 formed disordered molecular layers on Au, even though the molecule–surface bonding (thiolate) is the same as in the case of molecule 1. This suggests that the methylene linker in molecule 2 has a strong impact on the quality of the resulting film, so that a well-ordered SAM cannot be formed. The silane system, 3, is also able to bind to the gold surface but the resulting SAM has a poor quality, being significantly disordered and/or comprised of strongly inclined molecules. The above results suggest that the nature of the anchor group along with a possible linker is an important parameter which, to a high extent, predetermines the entire quality of OPE-based molecular layers.

  卟啉功能化低聚亚苯基乙炔基 (OPE) 是分子电子学应用中很有前景的分子。三个这样的分子（1-3）具有共同结构P-OPE-AG（P和AG分别是卟啉和锚定基团）和不同的锚定基团，即。已合成乙酰基保护的硫醇 –S–COCH3 (1)、带亚甲基连接基的乙酰基保护的硫醇 –CH2–S–COCH3 (2) 和三甲基甲硅烷基乙炔基 –CC–Si(CH3)3 (3)并在Au(111)基底上制备了相应的自组装单层(SAM)。通过X射线光电子能谱和近边X射线吸收精细结构光谱研究了这些薄膜的完整性和结构特性。结果表明，由 1 形成的薄膜具有高取向顺序，几乎垂直取向且分子成分紧密堆积，即代表了高质量的 SAM。相比之下，分子 2 在 Au 上形成无序分子层，尽管分子-表面键合（硫醇盐）与分子 1 的情况相同。这表明分子 2 中的亚甲基连接体对金的质量有很大影响。所得薄膜，从而无法形成良好有序的SAM。硅烷系统 3 也能够结合到金表面，但所得 SAM 质量较差，明显无序和/或由强烈倾斜的分子组成。上述结果表明，锚定基团的性质以及可能的连接体是一个重要参数，它在很大程度上预先确定了基于 OPE 的分子层的整体质量。
• Orthogonally Functionalized Oligomers for Controlled Self-Assembly
  作者：Austen K. Flatt、Yuxing Yao、Francisco Maya、James M. Tour

  DOI：10.1021/jo035821b

  日期：2004.3.1

  The synthesis of molecules terminated with complementary thiol-protecting groups is described. The target compounds contain functionalities on one end known to form self-assembled monolayers on metal surfaces while at the other end an intact thioacetate is present whereby self-assembly may again occur after an in situ deprotection. Self-assembly data is reported for selected compounds to assess their efficacy in surface adhesion.