4'-乙炔基苯并15-冠-5 | 92710-94-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 4'-乙炔基苯并15-冠-5
• 英文名称: 4'-(Ethynyl)benzo-15-crown-5
• 英文别名: 4-Ethynylbenzo-15-crown-5；17-ethynyl-2,5,8,11,14-pentaoxabicyclo[13.4.0]nonadeca-1(15),16,18-triene
• CAS: 92710-94-6
• 化学式: C₁₆H₂₀O₅
• 分子量: 292.332
• InChiKey: ATOWSSXTGDOERW-UHFFFAOYSA-N

物化性质

• 沸点：
  432.3±45.0 °C(Predicted)
• 密度：
  1.16±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  21
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  46.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  4'-乙炔基苯并15-冠-5 在 吡啶 、 copper diacetate 、 copper(l) chloride 作用下， 以 甲醇 为溶剂， 反应 48.0h， 以76.8%的产率得到1,4-bis(2,3,5,6,8,9,11,12-octahydro-1,4,7,10,13-pentaoxabenzocyclopentadecen-15-yl)buta-1,3-diyne
  参考文献：
  名称：

  The synthesis and structural characterization of the first bis(benzocrown ethers) with polyyne linkages †

  摘要：

  成功合成了双(苯并-15-冠醚-5)丁-1,3-二炔和双(苯并-15-冠醚-5)辛-1,3,5,7-四炔，并利用 X 射线晶体学对其进行了表征。此外，还研究了聚[双（苯并冠醚）二乙炔]的实验。

  DOI：

  10.1039/b001856m
• 作为产物：
  描述：

  15-iodo-2,3,5,6,8,9,11,12-octahydrobenzo[b][1,4,7,10,13]pentaoxacyclopentadecane 在 bis-triphenylphosphine-palladium(II) chloride 、 氢氧化钾 、 copper(l) iodide 、 三乙胺 作用下， 以 甲醇 、 苯 为溶剂， 反应 2.5h， 生成 4'-乙炔基苯并15-冠-5
  参考文献：
  名称：

  摘要：

  4 ' -Ethynylbenzo-12-crown-4 (8), 4 ' -ethynylbenzo-15-crown-5 (9), and 4 ' -ethynylbenzo-18-crown-6 (10) were synthesized by cross-coupling of the corresponding aryl iodides 1-3 with 2-methylbut-3-yn-2-ol (4a) followed by the retro-Favorsky cleavage of the resulting carbinols. Unlike the corresponding benzo-12-crown-4 derivative (5a), the cleavage of tertiary acetylenic, alcohols of benzo-15-crown-5 (6a) and benzo-18-crown-6 (7a) requires more than one molar equivalent of KOH. Aminoalkylation of crown ether 8 gives Mannich bases, independently of the reaction conditions and the nature of amine. The aminomethylation of acetylenic crown ethers 9 and 10 with paraform-piperidine (morpholine) in the presence of CuCl yields 1,4-disubstituted buta-1,3-diynes (19, 20) rather than Mannich bases.

  DOI：

  10.1023/a:1011367311643

文献信息

• New alkynyl- and vinyl-linked benzo- and aza-crown etherbipyridyl ruthenium(II) complexes which spectrochemically recognize Group IA and IIA metal cations
  作者：Paul D. Beer、Oldrich Kocian、Roger J. Mortimer、Christopher Ridgway

  DOI：10.1039/dt9930002629

  日期：——

  A new alkynyl-linked bis(benzo-15-crown-5) bipyridyl ligand and new mono- and bis-benzo-15-crown-5 and aza-15-crown-5 bipyridyl ligands containing trans-conjugated olefinic linkages between the crown ethers and the 4,4′-disubstituted 2,2′-bipyridine (bipy) moieties have been synthesised. The corresponding [RuL(bipy)2][PF6]2 and [RuL3][PF6]2 complexes have been prepared and the latter electropolymerized

  一种新的炔基联双（苯并-15-冠-5）联吡啶配体和新的单-和双-苯并-15-冠-5和含氮杂-15-冠-5联吡啶配体的反式-缀合的冠部之间的联系烯烃醚和4,4'-二取代的2,2'-联吡啶（联吡啶）部分已经合成。相应的[RuL（bipy）2 ] [PF 6 ] 2和[RuL 3 ] [PF 6 ] 2制备了配合物，并将后者电聚合到光学透明的导电玻璃电极上。电子吸收和荧光发射光谱测量表明，新型的官能化冠醚既可以作为溶液配合物，也可以作为聚合物膜，对IA和IIA类金属阳离子进行光谱化学识别。的λ最大值和Iμ值二者的基于配体的低能量π-π*跃迁以及用于复合物中观察到的金属到配体的电荷传输带对的钠和镁阳离子的结合敏感。光谱测量结果进一步证明了电聚合膜中残留不饱和键的存在，提供了一种可用于探测这种电聚合机理和效率的技术。
• A Diiminoplatinum( <scp>II</scp> ) Complex of 4‐Ethynylbenzo‐15‐crown‐5 as a Luminescent Sensor for Divalent Metal Ions
  作者：Phyllis K. M. Siu、Siu‐Wai Lai、Wei Lu、Nianyong Zhu、Chi‐Ming Che

  DOI：10.1002/ejic.200300214

  日期：2003.8

  diiminoplatinum(II) complex of 4-ethynylbenzo-15-crown-5 to divalent metal ions such as Mg2+ or Zn2+ is accompanied by substantial enhancement of emission intensity (1035- and 870-fold increase, respectively, with 40 equivalents of metal salt) at λmax ≈ 555 nm; H+, Cd2+ and alkali-metal ions cause minor enhancement of the photoluminescence (⩽ 10-fold) under similar conditions. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451

  4-ethynylbenzo-15-crown-5 的二亚氨基铂 (II) 络合物与二价金属离子如 Mg2+ 或 Zn2+ 的结合伴随着发射强度的显着增强（分别增加 1035 倍和 870 倍，40 当量）金属盐）在 λmax ≈ 555 nm；在类似条件下，H+、Cd2+ 和碱金属离子会导致光致发光的轻微增强（⩽ 10 倍）。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
• Nematic liquid crystal compounds containing a benzocrown ether unit
  作者：Gong-Xin He、Fumio Wada、Kiyoshi Kikukawa、Tsutomu Matsuda

  DOI：10.1039/c39870001294

  日期：——

  Benzocrown ethers carrying a para-substituted biphenyl group, (1a–c and 2a,b), display a nematic liquid crystal phase; selective complexation with picrates in the liquid crystal phase was observed by doping experiments.

  带有对位取代联苯基（1a – c和2a，b）的苯并冠醚显示出向列型液晶相。通过掺杂实验观察到在液晶相中与苦味酸盐的选择性络合。
• Syntheses, coordination, spectroscopy and electropolymerisation studies of new alkynyl and vinyl linked benzo- and aza-crown ether–bipyridyl ruthenium(<scp>II</scp>) complexes. Spectrochemical recognition of group IA/IIA metal cations
  作者：Paul D. Beer、Oldrich Kocian、Roger J. Mortimer、Christopher Ridgway

  DOI：10.1039/c39910001460

  日期：——

  New alkynyl and vinyl linked benzo- and aza-crown ether–bipyridyl ruthenium(II) complexes have been prepared and electropolymerised onto platinum and optically transparent conducting glass electrodes to produce novel films capable of spectrochemically recognising alkali and alkaline earth metal guest cations.

  新型炔基和乙烯基连接的苯并和氮杂冠醚-联吡啶钌(II)配合物已被制备并电聚合到铂和光学透明导电玻璃电极上，以产生能够通过光谱化学方法识别碱金属和碱土金属客体阳离子的新型薄膜。
• Design and synthesis of luminescence chemosensors based on alkynyl phosphine gold(i)–copper(i) aggregates
  作者：Xiaoming He、Nianyong Zhu、Vivian Wing-Wah Yam

  DOI：10.1039/c1dt10197h

  日期：——

  Receptor-containing polynuclear mixed-metal complexes of gold(I)–copper(I) 1–3 based on a [Au3Cu2(CCPh)6}Au3PPh2–C6H4–PPh2}3]2+ (Au6Cu2) core with benzo-15-crown-5, oligoether and urea binding sites were designed and synthesized, respectively. These complexes exhibited remarkably strong red emission at ca. 619–630 nm in dichloromethane solution at room temperature upon photoexcitation at λ > 400 nm, with the emission quantum yield in the range 0.59–0.85. The cation-binding properties of 1 and 2 and the anion-binding properties of 3 were studied using UV-vis, emission and 1H NMR techniques. Complex 1, with six benzo-15-crown-5 pendants, was found to show a higher binding preference for K+, with a selectivity trend of K+ ≫ Cs+ > Na+ > Li+. The addition of metal ions (Li+, Na+, K+ and Cs+) to complex 1 led to a modest emission enhancement with a concomitant slight blue shift in energy and well-defined isoemissive points, which is attributed to the rigidity of the structure and the inhibited PET (photo-induced electron transfer) process from the oxygen to the aggregate as a result of the binding of the metal ion. The six urea receptor groups on complex 3 were found to form multiple hydrogen bonding interactions with anions, with the positive charge providing additional electrostatic interaction for anion-binding. The anion selectivity of 3 follows the trend F− > Cl− ≈ H2PO4− > Br− and the highest affinity towards F− is attributed to the stronger basicity of F−, as well as its good size match with the cavity of the urea pocket.

  分别设计并合成了以[Au3Cu2(CCPh)6}Au3PPh2âC6H4âPPh2}3]2+（Au6Cu2）为核心、具有苯并-15-冠醚-5、寡聚醚和脲结合位点的含受体多核混合金属金（I）â铜（I）1â3配合物。这些配合物在约 619â630 纳米波长的波长范围内显示出明显的红色发射。在室温下的二氯甲烷溶液中，当光激发波长δ" > 400 nm时，这些复合物在约 619â630 nm处显示出明显的强红色发射，发射量子产率在 0.59â0.85 之间。利用紫外可见光、发射和 1H NMR 技术研究了 1 和 2 的阳离子结合特性以及 3 的阴离子结合特性。研究发现，含有六个苯并-15-冠醚-5 下垂物的络合物 1 对 K+ 具有更高的结合偏好，其选择性趋势为 K+ â"Cs+ > Na+ > Li+。在复合物 1 中加入金属离子（Li+、Na+、K+ 和 Cs+）后，发射率会适度提高，同时能量会发生轻微的蓝移，并出现明确的等离点，这归因于结构的刚性以及金属离子的结合抑制了从氧到聚集体的 PET（光诱导电子转移）过程。研究发现，复合物 3 上的六个脲受体基团与阴离子形成了多种氢键相互作用，正电荷为阴离子结合提供了额外的静电作用。复合物 3 对阴离子的选择性呈 Fâ > Clâ â H2PO4â > Brâ 的趋势，对 Fâ 的亲和力最高，这是因为 Fâ 的碱性较强，而且其大小与脲口袋的空腔相匹配。