1,8-bis(3-hydroxy-3-methylbutynyl)pyrene

• 分子结构分类: 有机化合物 - 苯类化合物 - 芘
• 英文名称: 1,8-bis(3-hydroxy-3-methylbutynyl)pyrene
• 英文别名: 2,2'-(Pyrene-1,8-diylbis(ethyne-2,1-diyl))bis(propan-2-ol)；4-[8-(3-hydroxy-3-methylbut-1-ynyl)pyren-1-yl]-2-methylbut-3-yn-2-ol
• 化学式: C₂₆H₂₂O₂
• 分子量: 366.459
• InChiKey: IMZHGAUTOXQBMM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  28
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1,8-bis(3-hydroxy-3-methylbutynyl)pyrene 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 三乙胺 、 三苯基膦 、 sodium hydroxide 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 27.0h， 生成 1,8-Bis[2-(2,5-didodecoxyphenyl)ethynyl]pyrene
  参考文献：
  名称：

  Synthesis and property studies of linear and kinked poly(pyreneethynylene)s

  摘要：

  A series of fluorescent conjugated polymers, poly(pyreneethynylene)s, have been designed and synthesized to investigate the effect of shape of polymer backbone on physical properties. Polymers with linear and kinked backbone were synthesized using 1,6- and 1,8-disubstituted pyrene. The target copolymers were designed to incorporate various spacer units, such as, alkoxyphenyl, carbazole and fluorene on the polymer backbone. Characterization of the target compounds was achieved by NMR, IR, GPC and MALDI-TOF mass spectrometry. Detailed investigation on their optical, electrochemical and thermal properties revealed significant contribution of the geometry of polymer backbone towards physical properties. Kinked backbone of cisoid-polymers was found to result in lower optical band gap, less negative E-HOMO and higher thermal stability as compared to their linear analogues, most probably due to the coiling of polymer chains. Comparison of the physical properties of the polymers with those of the model compounds suggested similar extent of conjugation through 1,6- and 1,8-position of pyrene. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.polymer.2010.09.012
• 作为产物：
  描述：

  芘 在 copper(l) iodide 、 四(三苯基膦)钯 、 氢溴酸 、 双氧水 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 二乙胺 为溶剂， 反应 21.0h， 生成 1,8-bis(3-hydroxy-3-methylbutynyl)pyrene
  参考文献：
  名称：

  以乙炔基-P部分为主要骨架的铂-乙醛有机胶凝剂的设计与制备

  摘要：

  合成并表征了一系列新的以乙炔基-re部分为主要骨架的铂-乙炔复合物。对这些络合物的吸收和发射光谱的研究表明，通过引入不同编号的铂-乙炔化物片段，分子大小的扩展可以有效地调节从UV到更长波长区域的吸收和发射谱带。此外，这些复合物的凝胶化特性通过“试管稳定转化”方法进行了研究。大多数新设计的乙炔铂化合物在某些经过测试的溶剂中均表现出稳定的凝胶形成性能。通过扫描电子显微镜（SEM）研究干凝胶的形态。此外，聚合过程中的J型程序集。更重要的是，我们发现，该复合物4-C6，4，和4-C18具有四个铂-乙炔化物的片段呈现的潜在应用作为发光有机金属凝胶。

  DOI：

  10.1002/chem.201202902

文献信息

• Drug delivery of lipophilic pyrenyl derivatives by encapsulation in a water soluble metalla-cage
  作者：Johan Mattsson、Olivier Zava、Anna K. Renfrew、Yoshihisa Sei、Kentaro Yamaguchi、Paul J. Dyson、Bruno Therrien

  DOI：10.1039/c0dt00436g

  日期：——

  The self-assembly of 2,4,6-tris(pyridin-4-yl)-1,3,5-triazine (tpt) triangular panels with p-cymene (p-PriC6H4Me) ruthenium building blocks and 2,5-dioxydo-1,4-benzoquinonato (dobq) bridges, in the presence of a functionalised pyrenyl derivative (pyrene–R), affords the triangular prismatic host–guest compounds [(pyrene–R) ⊂ Ru6(p-PriC6H4Me)6(tpt)2(dobq)3]6+ ([(pyrene–R) ⊂ 1]6+). The inclusion of eight mono-substituted pyrenyl derivatives including biologically relevant structures (a = 1-pyrenebutyric acid, b = 1-pyrenebutanol, c = 1-pyrenemethylamine, d = 1-pyrenemethylbutanoate, e = 1-(4,6-dichloro-1,3,5-triazin-2-yl)pyrene, f = N-hexadecylpyrene-1-sulfonamide, g = pyrenyl ethacrynic amide and h = 2-(pyren-1-ylmethylcarbamoyl) phenyl acetate), and a di-substituted pyrenyl derivative (i = 1,8-bis(3-methyl-butyn-1-yl-3-ol)pyrene), has been accomplished. The carceplex nature of these systems with the pyrenyl moiety being firmly encapsulated in the hydrophobic cavity of the cage with the functional groups pointing outwards was confirmed by NMR (1H, 2D, DOSY) spectroscopy and electrospray ionization mass spectrometry (ESI-MS). The cytotoxicities of these water-soluble compounds have been established using human ovarian A2780 cancer cells. All the host–guest systems are more cytotoxic than the empty cage itself [1][CF3SO3]6 (IC50 = 23 μM), the most active carceplex [f ⊂ 1][CF3SO3]6 is an order of magnitude more cytotoxic.

  在功能化的芘衍生物（pyrene–R）的存在下，2,4,6-三（吡啶-4-基）-1,3,5-三嗪（tpt）三角形面板与对伞花烃（p-PriC6H4Me）钌建筑块和2,5-二氧-1,4-苯醌酸（dobq）桥自组装，形成了三角棱柱宿主-客体化合物[(pyrene–R) ⊂ Ru6(p-PriC6H4Me)6(tpt)2(dobq)3]6+（[(pyrene–R) ⊂ 1]6+）。已经成功地纳入了八种单取代的芘衍生物，其中包括生物相关的结构（a = 1-芘丁酸，b = 1-芘丁醇，c = 1-芘甲胺，d = 1-芘甲丁酸酯，e = 1-（4,6-二氯-1,3,5-三嗪-2-基）芘，f = N-十六烷基芘-1-磺酰胺，g = 芘依他尼酸胺，h = 2-（芘-1-基甲氨酰基）苯乙酸酯），以及一种双取代的芘衍生物（i = 1,8-双（3-甲基-丁炔-1-基-3-醇）芘）。通过NMR（1H，2D，DOSY）光谱和电喷雾电离质谱（ESI-MS）证实了这些系统的笼状性质，芘基团牢固地封装在笼的疏水腔内，功能基团指向外部。这些水溶性化合物的细胞毒性已经使用人卵巢A2780癌细胞进行了确定。所有的宿主-客体系统的细胞毒性都比空笼本身[1][CF3SO3]6（IC50 = 23 μM）更强，其中最活跃的笼状化合物[f ⊂ 1][CF3SO3]6的细胞毒性高出一个数量级。
• Synthesis and Photophysical Properties of a Highly Fluorescent Ditopic Ligand Based on 1,6-Bis(ethynyl)pyrene as Central Aromatic Core
  作者：Stéphanie Leroy-Lhez、Frédéric Fages

  DOI：10.1002/ejoc.200500059

  日期：2005.7

  and purification of two regioisomers of a pyrene derivative containing two ethynyl groups―1,6- and 1,8-bis(ethynyl)pyrene―is described. The former compound was used as a building block for the stepwise synthesis of a highly conjugated, ditopic bis(2,2'-bipyridine) ligand (2) containing the pyrene nucleus at the central core. The fluorescence properties of ligand 2 are reported. (© Wiley-VCH Verlag GmbH

  描述了一种简单的合成路线，用于有效制备和纯化含有两个乙炔基的芘衍生物的两种区域异构体——1,6- 和 1,8-双（乙炔基）芘——。前一种化合物被用作逐步合成高度共轭的双位双 (2,2'-联吡啶) 配体 (2) 的构件 (2)，在中心核心含有芘核。报道了配体2的荧光特性。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
• A novel pyrene-containing fluorescent organogel derived from a quinoline-based fluorescent porbe: synthesis, sensing properties, and its aggregation behavior
  作者：Chang-Bo Huang、Li-Jun Chen、Junhai Huang、Lin Xu

  DOI：10.1039/c4ra02373k

  日期：——

  A new family of pyrene-containing compounds 2–4 derived from aminoquinoline-containing fluorescent probe 1 were successfully synthesized and well characterized. The investigation of the absorption and emission spectra of these compounds revealed that the photophysical properties were significantly affected by the substitution of pyrene. Moreover, these compounds exhibited selective fluorescence behaviour towards Zn2+ in aqueous solution. The gelation properties of these compounds were investigated by the “stable to inversion of a test tube” method. Interestingly, 1,8-bis-substituted compound 4 displayed stable gel-formation properties in acetone, dioxane, tetrahydrofuran, ethyl acetate, chloroform, and dichloromethane. The morphologies of the xerogels were investigated by scanning electron microscopy (SEM) and laser scanning confocal microscopy (LSCM). The concentration- and temperature-dependent emission properties, and concentration- and temperature-variable 1H NMR spectroscopy of compound 4 were investigated, which suggested that both π–π stacking interaction and hydrogen bonding were the driving forces for the process of self-aggregation and the gel formation. In addition, studies on the luminescence properties indicated that 4 had the ability to form a fluorescent organogel with interesting fluorescence behaviour. More importantly, it was found that compound 4 could form a stimuli-responsive gel that had a sensitive gel-to-sol transition response to heating or adding Zn2+.

  从含氨基喹啉的荧光探针1成功合成并表征了一类新的含芘化合物2-4。对这些化合物的吸收和发射光谱的研究表明，光物理性质显著受到芘取代的影响。此外，这些化合物在水溶液中对Zn2+展示了选择性的荧光行为。通过“测试管稳定反转”方法研究了这些化合物的凝胶化性质。有趣的是，1,8-双取代化合物4在丙酮、二氧六环、四氢呋喃、乙酸乙酯、氯仿和二氯甲烷中表现出稳定的凝胶形成性质。通过扫描电子显微镜（SEM）和激光扫描共聚焦显微镜（LSCM）研究了凝胶的形态。研究了化合物4的浓度依赖性和温度依赖性的发射性质，以及浓度和温度可变的1H NMR光谱，结果表明π–π堆积相互作用和氢键是自聚集和凝胶形成过程的驱动力。此外，对发光性质的研究表明，4具有形成具有有趣荧光行为的荧光有机凝胶的能力。更重要的是，发现化合物4能够形成刺激响应性凝胶，对加热或添加Zn2+具有敏感的凝胶-溶胶转变响应。
• Circularly polarized luminescence of chiral 1,8-naphthalimide-based pyrene fluorophore induced via supramolecular self-assembly
  作者：Shuai Liu、Fei Li、Yuxiang Wang、Xiaojing Li、Chengjian Zhu、Yixiang Cheng

  DOI：10.1039/c7tc01371j

  日期：——

  Herein, two pairs of chiral 1,8-naphthalimide-based enantiomers incorporating D/L-alanine and pyrene fluorophore moieties were designed and synthesized. The fluorescence emission gradually changes from bright-yellow to red when the fraction of the poor solvent methanol increases from 0 to 99 vol%. No obvious circular dichroism (CD) and circularly polarized luminescence (CPL) signals could be observed

  在此，设计并合成了两对结合有D / L-丙氨酸和pyr荧光团的手性1,8-萘二甲酰亚胺基对映体。当不良溶剂甲醇的比例从0体积％增加到99体积％时，荧光发射从亮黄色逐渐变为红色。在CHCl 3溶液中没有观察到明显的圆二色性（CD）和圆偏振发光（CPL）信号。有趣的是，与在f m时的D / L -2相比，D / L -1可以表现出更强的红色CPL响应信号。=总计状态为99％；这是由于通过分子间π-π相互作用在聚集状态下形成规则有序的自组装纳米网络。而且，光学各向异性因子（g lum）可以达到高达0.013的值。
• Effect of alkoxy terminal chain length on mesomorphism of 1,6-disubstituted pyrene-based hexacatenar liquid crystals: columnar phase control
  作者：Takuji Hirose、Hiroaki Takai、Mizuki Watabe、Hiroyuki Minamikawa、Tatsuya Tachikawa、Koichi Kodama、Mikio Yasutake

  DOI：10.1016/j.tet.2014.05.111

  日期：2014.8

  Synthesis and mesophase-transition behaviors of six 1,6-disubstituted pyrene-based hexacatenar liquid crystals 1(n) (n=8-18) are reported here. They were synthesized by the Sonogashira coupling between 1,6-diethynylpyrene and 2-bromothiophene bearing a trialkoxybenzoyl group. The phase-transition behavior was studied by differential scanning calorimetry and polarized optical microscopy; a few mesophase progressions, I-Col/I-X-Col and Col-Sm, were observed, where X was an optically isotropic but un-identified phase. The structures of Col(r), Col(h), and Sm phases were analyzed by the X-ray crystallography, and the effect of the terminal alkoxy chain length on the mesomorphism was evaluated. (C) 2014 Elsevier Ltd. All rights reserved.