25,27-bis(3-cyanopropoxy)-26,28-dihydroxycalix[4]arene | 314256-73-0

• 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-bis(3-cyanopropoxy)-26,28-dihydroxycalix[4]arene
• 英文别名: 4,4'-{[26,28-dihydroxypentacyclo[19.3.1.1(3,7).1(9,13).1(15,19)]octacosa-1(25),3(28),4,6,9(27),10,12,15(26),16,18,21,23-dodecaene-25,27-diyl]bis(oxy)}dibutanenitrile；4-[[27-(3-Cyanopropoxy)-26,28-dihydroxy-25-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-dodecaenyl]oxy]butanenitrile
• CAS: 314256-73-0；783357-13-1
• 化学式: C₃₆H₃₄N₂O₄
• 分子量: 558.677
• InChiKey: VPNNMHLVWFAPIY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7
• 重原子数：
  42
• 可旋转键数：
  8
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.28
• 拓扑面积：
  107
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  25,27-bis(3-cyanopropoxy)-26,28-dihydroxycalix[4]arene 在 titanium(IV) chloride tetrahydrofuran 、 盐酸 、 水 作用下， 以 甲苯 为溶剂， 反应 48.0h， 以53%的产率得到26,27,28-trihydroxy-25-(3-cyanopropyloxy)calix[4]arene
  参考文献：
  名称：

  Easy and Selective Method for the Synthesis of Various Mono-O-functionalized Calix[4]arenes: De-O-functionalization Using TiCl₄

  摘要：

  An efficient and selective method for the monofunctionalization of p-tert-butylcalix[4]arene is described A mono-de-O-functionalization of disubstituted p-tert-butylcalix[4]arenes using titanium tetrachloride was developed to synthesize a series of monosubstituted p-tert-butylcalix[4]arenes with the pendant functions being ethoxycarbonylmethyloxy, 3-ethoxycarbonylpropyloxy, cyanomethyloxy, 3-cyanopropyloxy, 4-bromobutyloxy, 3-hydroxypropyloxy, propyloxy, 2-methylpropyloxy, 3-butynyloxy, and 3-cyanopropyloxy groups The reaction mechanism of the formation of 5,11,17,23-tetra-tert-butyl-26,27,28-trihydroxy-25-(3-ethoxycarbonylpropyloxy) calix[4]arene was studied by H-1 NMR and GC/mass spectroscopy monitoring Reaction of TiCl4 with the disubstituted p-tert-butylcalix[4]arene produced the corresponding dioxocalix[4]arene titanium dichloride complex, which undergoes elimination of ethyl 4-chlorobutyrate, leading to a trioxocalix[4]arene titanium dichloride complex and to monosubstituted calix[4]arene after hydrolysis These two complexes were also synthesized, isolated, and fully characterized

  DOI：

  10.1021/jo101319s
• 作为产物：
  描述：

  5,11,17,23-tetra-t-butyl-25,26,27,28-tetrahydroxycalix-4-arene 在 aluminum (III) chloride 、 potassium carbonate 、 苯酚 作用下， 以 甲苯 、 乙腈 为溶剂， 生成 25,27-bis(3-cyanopropoxy)-26,28-dihydroxycalix[4]arene
  参考文献：
  名称：

  黄素-Calix [4]芳烃共轭衍生物的合成

  摘要：

  描述了两种新的黄素取代的杯[4]芳烃衍生物9和10的合成。第一个黄素取代的杯[4]亚芳基衍生物9是由3-甲基别恶嗪（5）与25,27-双（3-溴丙氧基）-26,28-二羟基-5,11,17,23-tetra反应合成的（叔丁基）杯[4]芳烃（4），收率高（92％）。另一种衍生物10是由3-甲基别恶嗪-1-乙酸（7）和25,27-双（3-氰基丙氧基）杯[4]芳烃（3）制备的。所有新化合物均通过FT-IR和1 H-NMR光谱结合元素分析技术进行表征。

  DOI：

  10.1002/hlca.201000260

文献信息

• First Synthesis and Structure of β-Ketoimine Calix[4]arenes: Complexation and Extraction Studies
  作者：Hatem Halouani、Isabelle Dumazet-Bonnamour、Monique Perrin、Roger Lamartine

  DOI：10.1021/jo0495485

  日期：2004.10.1

  β-ketoimine calix[4]arene derivatives is described. The reaction of calix[4]arene or p-tert-butylcalix[4]arene with bromoacetonitrile or bromobutyronitrile afforded di-, tri-, and tetranitrile calixarene derivatives (3−8, 3a), which were then reduced into the corresponding amine (9−13, 3b). The condensation of these aminocalixarenes with acetylacetone led to six β-ketoimine calix[4]arene derivatives (14−18

  描述了一系列新的β-酮亚胺杯[4]芳烃衍生物的合成。杯的反应[4]芳烃或p -叔-butylcalix [4]芳烃与溴乙腈或溴丁腈，得到二- ，三- ，和四腈杯芳烃衍生物（3 - 8，图3a），然后将其还原成相应的胺（9 - 13，图3b）。这些aminocalixarenes与乙酰丙酮的缩合导致6β酮亚胺杯[4]芳烃衍生物（14 - 18，图3c），为类朝向过渡金属选择性受体。分子结构4，通过X射线衍射确定了图7和图17。17的堆积揭示了分子内和分子间氢键的网络。受体的络合性能15，17，和图3c朝向不同的金属离子已被通过在有机介质中的UV-vis滴定研究。通过摩尔比法和Job图确定了具有17的配合物的化学计量。这些新颖的受体选择性地复合Cu 2 +，Hg 2+和Ag +。而且17的萃取性能通过液-液萃取和原子吸收光谱研究了对阳离子的反应。化合物17对Pb 2+具有良好的亲和性和选择性。
• Synthesis and characterization of a stable copper (I) calix[4]dicyano-diimidazole complex
  作者：Sebastien Noel、Hui Ren、Tao Tu、Erwann Jeanneau、Caroline Félix、Florent Perret、Francis Vocanson、Christophe Bucher、Guy Royal、Isabelle Bonnamour、Ulrich Darbost

  DOI：10.1016/j.tetlet.2012.06.065

  日期：2012.8

  A new calix[4]dicyano-diimidazole ligand was prepared in two steps from a de-tert-butylated calix[4]arene. The corresponding Cu (I) complex was found to be remarkably stable. The X-ray structure of the latter revealed a mixture of both monomeric-mononuclear and dimeric-dinuclear complexes. Detailed investigations on this copper complex, involving NMR (VT and DOSY), Infra-red, and MS analyses, demonstrated that the dimeric-dinuclear complexe does not exist in solution. Despite the presence of two cyano binding groups on the calixarene platform, every attempts to isolate a stable Cu(II) complex failed. (C) 2012 Elsevier Ltd. All rights reserved.
• Synthesis of Flavin-Calix[4]arene Conjugate Derivatives
  作者：Serkan Sayin、Gülderen Uysal Akkuş、Radek Cibulka、Ivan Stibor、Mustafa Yilmaz

  DOI：10.1002/hlca.201000260

  日期：2011.3

  The synthesis of two new flavin substituted calix[4]arene derivatives, 9 and 10, is described. The first flavin substituted calix[4]arene derivative 9 was synthesized by the reaction of 3‐methylalloxazine (5) with 25,27‐bis(3‐bromopropoxy)‐26,28‐dihydroxy‐5,11,17,23‐tetra(tert‐butyl)calix[4]arene (4) in high yield (92%). The other derivative 10 was prepared from 3‐methylalloxazine‐1‐acetic acid (7)

  描述了两种新的黄素取代的杯[4]芳烃衍生物9和10的合成。第一个黄素取代的杯[4]亚芳基衍生物9是由3-甲基别恶嗪（5）与25,27-双（3-溴丙氧基）-26,28-二羟基-5,11,17,23-tetra反应合成的（叔丁基）杯[4]芳烃（4），收率高（92％）。另一种衍生物10是由3-甲基别恶嗪-1-乙酸（7）和25,27-双（3-氰基丙氧基）杯[4]芳烃（3）制备的。所有新化合物均通过FT-IR和1 H-NMR光谱结合元素分析技术进行表征。
• Easy and Selective Method for the Synthesis of Various Mono-<i>O</i>-functionalized Calix[4]arenes: De-<i>O</i>-functionalization Using TiCl₄
  作者：Joackim Bois、Jeff Espinas、Ulrich Darbost、Caroline Felix、Christian Duchamp、Denis Bouchu、Mostafa Taoufik、Isabelle Bonnamour

  DOI：10.1021/jo101319s

  日期：2010.11.19

  An efficient and selective method for the monofunctionalization of p-tert-butylcalix[4]arene is described A mono-de-O-functionalization of disubstituted p-tert-butylcalix[4]arenes using titanium tetrachloride was developed to synthesize a series of monosubstituted p-tert-butylcalix[4]arenes with the pendant functions being ethoxycarbonylmethyloxy, 3-ethoxycarbonylpropyloxy, cyanomethyloxy, 3-cyanopropyloxy, 4-bromobutyloxy, 3-hydroxypropyloxy, propyloxy, 2-methylpropyloxy, 3-butynyloxy, and 3-cyanopropyloxy groups The reaction mechanism of the formation of 5,11,17,23-tetra-tert-butyl-26,27,28-trihydroxy-25-(3-ethoxycarbonylpropyloxy) calix[4]arene was studied by H-1 NMR and GC/mass spectroscopy monitoring Reaction of TiCl4 with the disubstituted p-tert-butylcalix[4]arene produced the corresponding dioxocalix[4]arene titanium dichloride complex, which undergoes elimination of ethyl 4-chlorobutyrate, leading to a trioxocalix[4]arene titanium dichloride complex and to monosubstituted calix[4]arene after hydrolysis These two complexes were also synthesized, isolated, and fully characterized