1-tert-butyl-3,5-bis[(trimethylsilyl)ethynyl]benzene | 254101-30-9

• 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: 1-tert-butyl-3,5-bis[(trimethylsilyl)ethynyl]benzene
• 英文别名: 1-tert-butyl-3,5-bis(trimethylsilanylethynyl)benzene；3,5-bis(trimethylsilylethynyl)-(tert-butyl)benzene；1,3-bis[(trimethylsilyl)ethynyl]-5-tertbutylbenzene；3,5-bis(trimethylsilylethynyl)-1-(tert-butyl)benzene；2-[3-Tert-butyl-5-(2-trimethylsilylethynyl)phenyl]ethynyl-trimethylsilane
• CAS: 254101-30-9
• 化学式: C₂₀H₃₀Si₂
• 分子量: 326.629
• InChiKey: TXNLKCSICZUMLP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.44
• 重原子数：
  22
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 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-tert-butyl-3,5-bis[(trimethylsilyl)ethynyl]benzene 在 potassium carbonate 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 3.0h， 以0.266 g的产率得到1-tert-butyl-3,5-diethynylbenzene
  参考文献：
  名称：

  具有卤素键和硫族键的异位大环的卤化锂离子对识别

  摘要：

  一系列含有异位大环受体的卤素键和硫族元素键合的邻菲咯啉对卤化锂（LiX）离子对具有协同识别作用。CDCl 3  ：CD 3中的1 H NMR离子对定量定量滴定实验CN（1：1，v / v）揭示了卤离子与阴离子的结合，尤其是与卤素键合主体系统的共键合锂离子开关。双碘和碲甲基三唑的σ-孔供体基序的使用赋予了卤化物阴离子选择性和结合亲和力相反的特性，其中卤素键合双位主体能够完全结合氯化锂，而硫族元素键合对位受体对碘化锂显示出显着的选择性。溴化锂。初步的固液萃取实验表明，σ孔介导的离子对识别是锂盐回收的一种有前途的策略。

  DOI：

  10.1039/d1cc01287h
• 作为产物：
  描述：

  4-tert-butyl-2,6-diiodoaniline 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 硫酸 、 溶剂黄146 、 三乙胺 、 sodium nitrite 作用下， 以 四氢呋喃 为溶剂， 反应 24.5h， 生成 1-tert-butyl-3,5-bis[(trimethylsilyl)ethynyl]benzene
  参考文献：
  名称：

  卤素键诱导的三重螺旋封装了碘化物

  摘要：

  高阶阴离子螺旋在溶液中的自组装仍然是一个难以实现的目标。在此，我们提出了第一个将碘化物封装在有机和水介质以及固态中的三螺旋结构。三螺旋由三个三阳离子芳基乙炔基链自组装而成，类似于排列有九个卤素键供体的管状阴离子通道。八个强碘···碘化物卤素键和大量埋入的 π 表面赋予三链体即使在高温下也具有显着的稳定性。我们认为单链螺旋的自然上升使其线性卤素键供体不收敛。因此，卤素键的严格线性是合成多链阴离子螺旋的有力工具。

  DOI：

  10.1002/anie.201605440

文献信息

• Aromatic and Aliphatic CH Hydrogen Bonds Fight for Chloride while Competing Alongside Ion Pairing within Triazolophanes
  作者：Yuran Hua、Raghunath O. Ramabhadran、Esther O. Uduehi、Jonathan A. Karty、Krishnan Raghavachari、Amar H. Flood

  DOI：10.1002/chem.201002340

  日期：2011.1.3

  Triazolophanes are used as the venue to compete an aliphatic propylene CH hydrogen‐bond donor against an aromatic phenylene one. Longer aliphatic CH⋅⋅⋅Cl− hydrogen bonds were calculated from the location of the chloride within the propylene‐based triazolophane. The gas‐phase energetics of chloride binding (ΔGbind, ΔHbind, ΔSbind) and the configurational entropy (ΔSconfig) were computed by taking all

  三唑烷用作竞争脂肪族丙烯CH氢键供体与芳香亚苯基竞争的场所。更长的脂肪族的C  ħ ⋅⋅⋅氯-氢键从的基于丙烯的triazolophane内氯化物的位置计算。通过考虑所有低能构象，计算出氯离子结合的气相能（ΔG结合，ΔH结合，ΔS结合）和构型熵（ΔS config）。从Δ结合降低所计算的气相自由能的亚苯基和基于丙烯的triazolophanes节目之间的比较ģ绑定= -194到-182千焦摩尔-1，分别与适度的焓-比熵的补偿。对这些差异进行了实验研究。的1 H NMR光谱对丙烯triazolophane的结构研究的1：1个的氯化物络合物是用较弱的丙烯CH氢键相一致。为了量化在二氯甲烷两个triazolophanes之间的亲和力的差异，这是至关重要的，以获得准确的结合模型。确定了四个平衡点。除了1：1个复合及2:1夹心形成，所述四丁基氯化铵盐（TBA的离子配对+ ⋅氯- ）和阳离子配对的TBA
• A Long‐Lived Halogen‐Bonding Anion Triple Helicate Accommodates Rapid Guest Exchange
  作者：Casey J. Massena、Daniel A. Decato、Orion B. Berryman

  DOI：10.1002/anie.201810415

  日期：2018.12.3

  milliseconds or faster as determined by stopped‐flow visible spectroscopy. Additionally, the helicate accommodated bromide in solution and the solid state, while the thermodynamic stability of the triplex favored larger halide ions (bromide≈iodide≫chloride). Taken together, we elucidate a new class of kinetically stable helicates. These anion‐switchable triplexes maintain their architectures while accommodating

  阴离子模板螺旋结构正在成为一类动态且易于处理的超分子，其表现出阴离子可切换的自组装能力。我们首次利用卤素键合的间亚芳基-乙炔基低聚物对阴离子螺旋进行动力学研究。这些配体在溶液中形成高保真三螺旋，即使在高温下也具有令人惊讶的长寿命（数秒数量级）。我们提出了一种在同一时间尺度上缓慢进行的缔合配体交换机制。相比之下，通道内阴离子交换在几毫秒内迅速发生，或者根据停流可见光谱测定的更快。此外，螺旋结构可容纳溶液和固态的溴化物，而三链体的热力学稳定性有利于较大的卤化物离子（溴化物≈碘化物≫氯化物）。综上所述，我们阐明了一类新的动力学稳定的螺旋。这些阴离子可切换的三联体保持其架构，同时适应快速的通道内客体交换。
• Cross-Conjugated Bis(porphryin)s:  Synthesis, Electrochemical Behavior, Mixed Valency, and Biradical Dication Formation
  作者：David A. Shultz、Hyoyoung Lee、R. Krishna Kumar、Kevin P. Gwaltney

  DOI：10.1021/jo991046h

  日期：1999.12.1

  The synthesis and characterization of seven (Zn-II)(2)bis(porphyrin) molecules are described. The molecular structures of two bis(porphyrin)s (6 and 7) were determined by X-ray diffraction methods. Four of the compounds have their porphyrin moieties attached in a meta-fashion to a substituted benzene ring (1-4), two have porphyrin rings attached in a gem-fashion to a carbon- carbon double bond (6 and 7), and one bis(porphyrin) (5) has a p-phenylene coupler. Bis(porphyrin)s 1, 4, and 5 contain tetraaryl-type porphyrins, while 2, 3, 6, and 7 contain triarylethynylporphyrins. Except for exciton coupling in the unoxidized species, interaction between porphyrins is greater in the triarylethynyl-type bis(porphyrin)s than in the tetraaryl-type bis(porphyrin)s regardless of the number of bonds through which the interaction propagates. The cyclic volammetry of the bis(porphyrin)s was examined, and a varying degree of interaction between electrophores within the series was found. Redox splitting was observed for porphyrin ring oxidations of 3, 6, and 7, suggesting interaction between the oxidized porphyrin rings beyond simple electrostatic repulsions. No such redox splitting was observed for any of the tetraaryl-type bis(porphyrin)s (1, 4, and 5). We conclude that two porphyrin radical cations interact best when (1) the interaction pathway is short (Delta E-1/2(6/7) > Delta E-1/2(2/3)), (2) pi-overlap between the electrophore and coupler is maximized (minimal bond torsions: Delta E-1/2(6/7) > Delta E-1/2(4/5)), and (3) the electron demand of the coupler matches that of the spin carrier (Delta E-1/2(3) > Delta E-1/2(2)). One-electron oxidized triarylethynyl-type bis(porphyrin)s exhibit spectral features characteristic of mixed-valent compounds. In two cases (6(.+) and 7(.+)), near-IR bands near 8300 cm(-1) were observed and are tentatively assigned to intervalence transitions. Singly oxidized tetraaryl-type bis(porphyrin)s exhibit no such near-IR transitions, and electronic absorption spectra recorded during electrochemical oxidations are marked by isosbestic points, suggesting negligible interaction between the two halves of the molecule, consistent with cyclic voltammetric results. Two-electron oxidation of 2-7 yields biradical dications whose frozen solution EPR spectra lack fine structure, but exhibit Delta m(s) = 2 transitions characteristic of exchange-coupled S = 1 states. Oxidation of 1 yields a biradical in which both exchange coupling and dipolar interaction between unpaired electrons are presumably very weak; consequently no Delta m(s) = 2 is observed. The results of variable-temperature EPR spectroscopy of 2(2.2+)-7(2.2+) suggest either a triplet ground state or a singlet-triplet degeneracy. As a consequence of our results, we hypothesize that the exchange interaction, and therefore the singlet-triplet gap, in a biradical di-ion can be adjusted to favor the triplet state by simple substituent effects.
• Facile Intramolecular Cyclization in Oxidative Coupling of Acetylenes Linked to 1,3-Positions of Benzene:  Strained [12]Metacyclophanedienetetrayne System
  作者：Yoshito Tobe、Jun-ya Kishi、Ichiro Ohki、Motohiro Sonoda

  DOI：10.1021/jo0268299

  日期：2003.4.1

  Oxidative coupling of ethynylpropellane linked to 1,3,5-position of a benzene core 3b did not give the cage dimer 2 but the dimer 4 having a strained [12]metacyclo-phanedienetetrayne system. The spectral and structural features of the novel ring system were revealed for the simple dibenzo derivative 6, which was also prepared efficiently by the intramolecular cyclization of the open-chain precursor.