2'-carboxy-4,4''-bis(ethynyl)-5'-(1-octynyl)-1,1':3',1''-terphenyl | 1034710-51-4

• 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: 2'-carboxy-4,4''-bis(ethynyl)-5'-(1-octynyl)-1,1':3',1''-terphenyl
• 英文别名: 2,6-Bis(4-ethynylphenyl)-4-oct-1-ynylbenzoic acid；2,6-bis(4-ethynylphenyl)-4-oct-1-ynylbenzoic acid
• CAS: 1034710-51-4
• 化学式: C₃₁H₂₆O₂
• 分子量: 430.546
• InChiKey: LFUNHTBDQSJSJA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.6
• 重原子数：
  33
• 可旋转键数：
  10
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.19
• 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：

  2'-carboxy-4,4''-bis(ethynyl)-5'-(1-octynyl)-1,1':3',1''-terphenyl 在 copper(l) iodide 、 四(三苯基膦)钯 、 1-羟基苯并三唑 、 盐酸-N-乙基-Nˊ-(3-二甲氨基丙基)碳二亚胺 、 二异丙胺 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 24.0h， 生成
  参考文献：
  名称：

  带有催化非对称羟醛反应的非手性双官能团的互补双链螺旋低聚物。

  摘要：

  两个新型手性二聚体和三聚体链构成的米-三联苯基团通过连接p合成了分别在链末端或中心引入手性am基和非手性哌嗪基的二乙炔基苯单元，及其互补的非手性羧酸二聚体和三聚体。互补的手性/非手性链形成过度使用的双螺旋结构，在手性am基-羧酸盐盐桥偏向的共轭主链的吸收区域中，强烈的分裂型棉花效应支持了这种作用。尽管中间引入的具有催化活性的双功能哌嗪/羧酸对是非手性的，但发现双螺旋三聚体可催化环己酮与4-硝基苯甲醛的直接羟醛反应，并产生具有中等对映选择性的产物。

  DOI：

  10.1002/chir.23169
• 作为产物：
  描述：

  2'-carboxy-4,4''-bis(trimethylsilylethynyl)-5'-(1-octynyl)-1,1':3',1''-terphenyl 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 生成 2'-carboxy-4,4''-bis(ethynyl)-5'-(1-octynyl)-1,1':3',1''-terphenyl 、 2'-carboxy-4-ethynyl-4''-trimethylsilylethynyl-5'-(1-octynyl)-1,1':3',1''-terphenyl
  参考文献：
  名称：

  带有羧基的共轭聚合物的同质双螺旋的形成和夹在链间的手性胺对大分子螺旋度的放大作用

  摘要：

  夹心胺：具有羧基的π共轭聚合物可自缔合形成消旋双螺旋。相反，与手性胺形成一个独特的单手双螺旋，其中的链通过环状氢键网络将成对的手性胺夹在中间（见图）。胺的手性信息随着螺旋手性的显着放大而转移到聚合物主链上。

  DOI：

  10.1002/anie.201301005

文献信息

• Remarkable acceleration of template-directed photodimerisation of 9-phenylethynylanthracene derivatives assisted by complementary salt bridge formation
  作者：Junki Tanabe、Daisuke Taura、Naoki Ousaka、Eiji Yashima

  DOI：10.1039/c6ob02087a

  日期：——

  acid monomers bearing a 9-phenylethynylanthracene unit at one and both ends were further investigated in the presence and absence of the complementary amidine dimer as the template. It was found that a similar photooxidation reaction of the monomers was significantly suppressed in the presence of the template even in undegassed chloroform. In addition, the template-directed photodimerisation of the mono-

  在脱气的氯仿和苯中对9-苯基乙炔基蒽的光照射不仅提供了[4 + 2]-抗Diels-Alder加成二聚体，而且还提供了[4 + 4]-抗单晶X射线分析首次发现，β-二聚体是次要产物，而蒽残基在未脱气的稀氯仿中被定量氧化，得到相应的内过氧化物。在存在和不存在互补am二聚体作为模板的情况下，进一步研究了在一端和两端带有9-苯基乙炔基蒽单元的羧酸单体的光化学反应。发现在模板存在下，即使在未脱氯的氯仿中，单体的类似光氧化反应也被显着抑制。此外，在脱气的氯仿中，单-和二-9-苯基乙炔基蒽的结合单体的模板定向光二聚反应显着加速了30倍或61倍，得到了[4 + 2]-抗-和[4 + 4]-抗-二聚体分别作为主要产物和次要产物，而在没有模板的情况下，优先使与二-9-苯基乙炔基蒽结合的单体进行光聚合。
• Double-Stranded Helical Polymers Consisting of Complementary Homopolymers
  作者：Takeshi Maeda、Yoshio Furusho、Shin-Ichiro Sakurai、Jiro Kumaki、Kento Okoshi、Eiji Yashima

  DOI：10.1021/ja711447s

  日期：2008.6.1

  Two complementary homopolymers of chiral amidines and achiral carboxylic acids with m-terphenyl-based backbones were synthesized by the copolymerization of a p-diiodobenzene derivative with the diethynyl monomers bearing a chiral amidine group and a carboxyl group using the Sonogashira reaction, respectively. Upon mixing in THF, the homopolymer strands assembled into a preferred-handed double helix through interstrand amidinium-carboxylate salt bridges, as evidenced by its absorption, circular dichroism, and IR spectra. In contrast, when mixed in less polar solvents, such as chloroform, the complementary strands kinetically formed an interpolymer complex with an imperfect double helical structure containing a randomly hybridized cross-linked structure, probably because of strong salt bridge formations. This primary complex was rearranged into the fully double helical structure by treatment with a strong acid followed by neutralization with an amine. High-resolution atomic force microscopy revealed the double-stranded helical structure and enabled the determination of the helical sense.
• Sequence- and Chain-Length-Specific Complementary Double-Helix Formation
  作者：Hiroshi Ito、Yoshio Furusho、Toshihide Hasegawa、Eiji Yashima

  DOI：10.1021/ja806194e

  日期：2008.10.22

  The artificial sequential strands consisting of two, three, or four m-terphenyl groups joined by diacetylene linkers with complementary binding sites, either the chiral amidine (A) or achiral carboxyl (C) group, were synthesized in a stepwise manner. Using circular dichroism and H-1 NMR spectroscopies along with liquid chromatography, we showed that, when three dimeric molecular strands (AA, CC, and AC) or six trimeric molecular strands (AAA, CCC, AAC, CCA, ACA, and CAC) were mixed in solution, the complementary strands were sequence-specifically hybridized to form one-handed double-helical dimers AA center dot CC and (AC)(2) or trimers AAA center dot CCC, AAC center dot CCA, and ACA center dot CAC, respectively, through complementary amidinium-carboxylate salt bridges. Upon the addition of CCA to a mixture of AAA, AAC, and ACA, the AAC center dot CCA double helix was selectively formed and then isolated from the mixture by chromatography. Moreover, the homo-oligomer mixtures of amidine or carboxylic acid from the monomers to tetramers (A, AA, AAAA, C, CC, and CCCC) assembled with a precise chain length specificity to form A center dot C, AA center dot CC, and AAAA center dot CCCC, which were separated by chromatography.
• Formation of a Homo Double Helix of a Conjugated Polymer with Carboxy Groups and Amplification of the Macromolecular Helicity by Chiral Amines Sandwiched between the Strands
  作者：Wataru Makiguchi、Shinzo Kobayashi、Yoshio Furusho、Eiji Yashima

  DOI：10.1002/anie.201301005

  日期：2013.5.10

  Sandwiched amines: A π‐conjugated polymer with carboxy groups self‐associates to form a racemic double helix. In contrast, with chiral amines it forms a unique one‐handed double helix, in which the strands sandwich pairs of chiral amines through cyclic hydrogen‐bonding networks (see picture). The chiral information of the amines is transferred to the polymer backbones with remarkable amplification

  夹心胺：具有羧基的π共轭聚合物可自缔合形成消旋双螺旋。相反，与手性胺形成一个独特的单手双螺旋，其中的链通过环状氢键网络将成对的手性胺夹在中间（见图）。胺的手性信息随着螺旋手性的显着放大而转移到聚合物主链上。
• Complementary double‐stranded helical oligomers bearing achiral bifunctional groups that catalyze asymmetric aldol reaction
  作者：Daisuke Taura、Kouhei Shimomura、Naoki Ousaka、Eiji Yashima

  DOI：10.1002/chir.23169

  日期：2020.3

  Two novel chiral dimer and trimer strands composed of m‐terphenyl groups linked through p‐diethynylbenzene units with the chiral amidine group and achiral piperazine group introduced at the terminus or center of the strands, respectively, and its complementary achiral carboxylic acid dimer and trimer were synthesized. The complementary chiral/achiral strands form an excess‐handed double‐helical structure

  两个新型手性二聚体和三聚体链构成的米-三联苯基团通过连接p合成了分别在链末端或中心引入手性am基和非手性哌嗪基的二乙炔基苯单元，及其互补的非手性羧酸二聚体和三聚体。互补的手性/非手性链形成过度使用的双螺旋结构，在手性am基-羧酸盐盐桥偏向的共轭主链的吸收区域中，强烈的分裂型棉花效应支持了这种作用。尽管中间引入的具有催化活性的双功能哌嗪/羧酸对是非手性的，但发现双螺旋三聚体可催化环己酮与4-硝基苯甲醛的直接羟醛反应，并产生具有中等对映选择性的产物。