25,27-dipropargyloxy-26,28-dihydroxy-calix[4]arene | 178116-64-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 25,27-dipropargyloxy-26,28-dihydroxy-calix[4]arene
• 英文别名: 25,27-Dipropargyloxy-26,28-dihydroxycalix[4]arene；26,28-bis(prop-2-ynoxy)pentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(25),3(28),4,6,9(27),10,12,15,17,19(26),21,23-dodecaene-25,27-diol
• CAS: 178116-64-8
• 化学式: C₃₄H₂₈O₄
• 分子量: 500.594
• InChiKey: FTCQEBYRZKHALU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.1
• 重原子数：
  38
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  58.9
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  25,27-dipropargyloxy-26,28-dihydroxy-calix[4]arene 在 硝酸 、 一水合肼 作用下， 以 二氯甲烷 、 二甲基亚砜 为溶剂， 反应 20.5h， 生成 5,17-diamino-25,26,27,28-tetrahydroxycalix[4]arene
  参考文献：
  名称：

  肼辅助的一锅去炔丙基化和功能化硝基杯[4]芳烃的还原

  摘要：

  含有两个或四个O-炔丙基部分的杯 [4] 芳烃衍生物能够在水合肼的存在下进行还原去炔丙基化。炔丙基以 4,5-二氢-1H-吡唑的形式被去除，这允许为去炔丙基化提出合理的机制。炔丙基可作为二-O-炔丙基取代的杯[4]芳烃和对-叔上环末端选择性硝化的保护剂-丁基杯[4]芳烃。在将镍催化剂添加到具有水合肼的反应混合物中后，硝基在上边缘的还原与去炔丙基化一起进行，这导致含有游离羟基的杯芳胺。

  DOI：

  10.1007/s11172-023-3858-4
• 作为产物：
  描述：

  杯[4]芳烃 、 3-溴丙炔 在 potassium carbonate 作用下， 以 丙酮 为溶剂， 反应 49.0h， 以55%的产率得到25,27-dipropargyloxy-26,28-dihydroxy-calix[4]arene
  参考文献：
  名称：

  Naphthyl “capped” triazole-linked calix[4]arene hosts as fluorescent chemosensors towards Fe³⁺and Hg²⁺: an experimental and DFT computational study

  摘要：

  四个新的“帽子”1,2,3-三唑连接受体6a–d的金属结合性质已报道。

  DOI：

  10.1039/c5nj01362c

文献信息

• Different sensing modes of fluoride and acetate based on a calix[4]arene with 25,27-bistriazolylmethylpyrenylacetamides
  作者：Hao-Chih Hung、Yung-Yu Chang、Liyang Luo、Chen-Hsiung Hung、Eric Wei-Guang Diau、Wen-Sheng Chung

  DOI：10.1039/c3pp50175b

  日期：2014.2

  25,27-Bis1′- N-(1-pyrenyl)-aminocarbonylmethyl-1 H-[1′,2′,3′]tri-azolyl-4′-methoxy-26,28-dihydroxycalix[4]arene, 4, is synthesized as a fluorescent chemosensor for the selective detection of both anions and ion pairs in MeCN. Sensor 4 uses bis-triazoles as ligands to bind a metal ion, bis-amides and bis-triazoles as the sites to recognize anions, and pyrenes as fluorophores. Among eight anions screened, chemosensor 4 showed a marked fluorescence change toward F−, H2PO4− and AcO−, but 4 responded to each anion in a distinct way. In the presence of F− at low concentrations, the dynamic excimer emission of compound 4 at λmax 482 nm was quenched, but an emission at λmax 472 nm appeared at large doses of F−. A control compound 6 showed very similar red shifts in the UV-vis and excitation spectra as 4 did, and its 472 nm emission band grew as the fluoride doses increased. Thus, the growth of the 472 nm emission of 4 and 6 in the presence of excess F− may be because strong H-bonding interactions of amido protons with F− favoured the formation of pyrene dimers in the ground state with charge transfer characteristics. The addition of H2PO4−, unlike F−, to a solution of 4 showed an enhanced monomer emission but a decreased excimer emission (λmax 482 nm). Adding AcO− to 4 produced a systematic change from a dynamic excimer (λmax 482 nm) to λmax 472 nm but with very little change in the UV-vis spectrum. Time-resolved fluorescence measurements on compound 6 with F− and AcO− confirmed that the 472 nm emission band mainly came from static excimers for the former, but was partly from a dynamic excimer for the latter because it contained a growth component in the fluorescence decay traces. Without pre-treatment with an anion, chemosensor 4 showed recognition of only metal ions Cu2+, Hg2+ and Cr3+, but it became sensitive to Ag+ when it was pretreated with fluoride.

  25,27-双1′-N-(1-芘基)-氨基甲酰基甲基-1H-[1′,2′,3′]三唑基-4′-甲氧基-26,28-二羟基杯芳烃，4，被合成为选择性检测MeCN中阴离子和离子对的荧光化学传感器。传感器4使用双三唑作为配体来结合金属离子，使用双酰胺和双三唑作为识别阴离子的位置，芘作为荧光基团。在筛选的八种阴离子中，化学传感器4对F−、H2PO4−和AcO−表现出显著的荧光变化，但4对每种阴离子的响应方式各不相同。在低浓度下，F−存在时化合物4在λmax 482 nm的动态外消旋发射被猝灭，但在高浓度F−下则出现λmax 472 nm的发射。一种对照化合物6在UV-vis和激发光谱上显示出与4非常相似的红移，其472 nm发射带随着氟离子剂量的增加而增强。因此，4和6在过量F−存在下472 nm发射的增强可能是由于氨基质子与F−之间强的氢键相互作用促进了基态下带有电荷转移特征的芘二聚体的形成。与F−不同，向4的溶液中加入H2PO4−显示增强的单体发射，但外消旋发射（λmax 482 nm）减弱。向4中加入AcO−产生了从动态外消旋（λmax 482 nm）到λmax 472 nm的系统性变化，但在UV-vis光谱中变化很小。对化合物6进行时间分辨荧光测量，发现472 nm的发射带主要来自于前者的静态外消旋，而后者则部分来自动态外消旋，因为在荧光衰减曲线中包含了生长成分。在未进行阴离子预处理的情况下，化学传感器4仅识别金属离子Cu2+、Hg2+和Cr3+，但在预处理氟离子后则对Ag+变得敏感。
• Cooperative Recognition of a Copper Cation and Anion by a Calix[4]arene Substituted at the Lower Rim by a β-Amino-α,β-Unsaturated Ketone
  作者：Annamalai Senthilvelan、I.-Ting Ho、Kai-Chi Chang、Gene-Hsiang Lee、Yi-Hung Liu、Wen-Sheng Chung

  DOI：10.1002/chem.200802654

  日期：2009.6.15

  Chemodosimeter: Upon titration with CuII, the fluorescence of 1 showed strong fluorescence enhancement because the metal ion helps to lock the conformation of the fluorophores. CuII was reduced to CuI by the free phenolic OH group of 1, the phenol was then oxidised by CuII and assisted in the trapping of CuI. Ditopic behaviour was observed for 1⋅CuI, which showed further enhancement of its fluorescence

  化学光度计：用Cu II滴定后，1的荧光显示出较强的荧光增强，因为金属离子有助于锁定荧光团的构象。Cu II被1的游离酚羟基还原为Cu I，然后苯酚被Cu II氧化，并辅助了Cu I的捕集。观察到双中心行为1⋅铜我，这表明在复合其荧光强度与阴离子的进一步增强（如所描绘，A - = CH 3 COO -或F - ）。
• Triazole-Modified Calix[4]crown as a Novel Fluorescent On−Off Switchable Chemosensor
  作者：Kai-Chi Chang、In-Hao Su、Annamalai Senthilvelan、Wen-Sheng Chung

  DOI：10.1021/ol071337+

  日期：2007.8.1

  A novel fluorescent on-off switchable chemosensor 1 with two different types of cationic binding sites is synthesized, which is composed of a triazole-modified calix[4]crown in the 1,3-alternate conformation. Among 15 metal ions examined, the fluorescence of 1 was strongly quenched by Hg2+, Cu2+, Cr3+, and Pb2+; however, the revival of emission from the strongly quenched 1.Pb2+ complex was achievable

  合成了具有两种不同类型阳离子结合位点的新型荧光开关化学传感器1，该传感器由1,3-交替构象的三唑修饰的杯[4]冠组成。在检查的15种金属离子中，1的荧光被Hg2 +，Cu2 +，Cr3 +和Pb2 +强烈淬灭；但是，通过添加K +，Ba2 +或Zn2 +离子可以实现强淬灭1.Pb2 +配合物的发射恢复。因此，金属离子交换可以触发开-关可切换的荧光化学传感器。
• Calix[4]arenes bearing triazolyl anthracenes: Hg²⁺-selective receptors exhibiting fluorescence or dual optical responses
  作者：Seung Hyeon Kim、Jaehyeon Kim、Sung Kuk Kim

  DOI：10.1039/d1nj03753f

  日期：——

  Calix[4]arenes 1 and 2 bearing two diametrical triazolyl anthracenes on the lower rim have been synthesized as a dual optical sensor and a fluorogenic cation sensor, respectively. UV/vis spectroscopy and fluorescence spectroscopy analyses revealed that receptors 1 and 2 are able to recognize divalent cations such as Ca2+, Zn2+, Ba2+, Hg2+, and Pb2+ with a significantly higher preference for Hg2+, giving

  杯[4]芳烃1和2在下边缘带有两个直径的三唑基蒽，分别合成为双光学传感器和荧光阳离子传感器。UV/vis 光谱和荧光光谱分析表明，受体1和2能够识别二价阳离子，例如 Ca 2+、Zn 2+、Ba 2+、Hg 2+和 Pb 2+，对 Hg 2 的偏好明显更高+，产生不同的颜色和荧光变化。也得到了证实1在乙腈中进行的 H NMR 光谱和荧光光谱分析表明，受体1通过不同的结合模式与阳离子结合，从而产生不同的比色和荧光响应。
• A Bifunctional Chromogenic Calix[4]arene Chemosensor for Both Cations and Anions: A Potential Ca2+ and F- Switched INHIBIT Logic Gate with a YES Logic Function
  作者：Kai-Chi Chang、In-Hao Su、Yu-Yun Wang、Wen-Sheng Chung

  DOI：10.1002/ejoc.201000581

  日期：2010.8

  A bifunctional chromogenic calix[4]arene 3, which contains both triazoles and hydroxy azophenols as both cationic and anionic recognition sites and the azophenol moiety as a coloration unit, was designed and synthesized. The recognition of Ca 2+ by 3 gave rise to a marked colour change from greenish to bright yellow, whereas the recognition of F - by 3 showed a colour change from light green to bluish

  设计并合成了双功能显色杯[4]芳烃3，它含有三唑和羟基偶氮酚作为阳离子和阴离子识别位点，偶氮酚部分作为着色单元。Ca 2+ by 3 的识别引起了明显的颜色变化，从绿色变为亮黄色，而 F - by 3 的识别显示了颜色从浅绿色变为蓝色。Ca 2+ 和F - 的输入实现了3的颜色变化，构建了分子水平的组合逻辑电路。