5-hydroxymethylene-1,3-phenylene-1',3'-phenylene-32-crown-10 | 191211-56-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 5-hydroxymethylene-1,3-phenylene-1',3'-phenylene-32-crown-10
• 英文别名: 5-(hydroxymethyl)-1,3-phenylene-1',3'-phenylene-32-crown-10；m-phenylene-5'-hydroxymethyl-1',3'-phenylene-32-crown-10；5-(hydroxymethyl)-1,3-phenylene-m-phenylene-32-crown-10；2,5,8,11,14,20,23,26,29,32-Decaoxatricyclo[31.3.1.115,19]octatriaconta-1(37),15(38),16,18,33,35-hexaen-17-ylmethanol
• CAS: 191211-56-0
• 化学式: C₂₉H₄₂O₁₁
• 分子量: 566.646
• InChiKey: BAZZRRXYDJAAKL-UHFFFAOYSA-N

物化性质

• 沸点：
  744.3±60.0 °C(Predicted)
• 密度：
  1.098±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  40
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  113
• 氢给体数：
  1
• 氢受体数：
  11

反应信息

• 作为反应物：
  描述：

  5-hydroxymethylene-1,3-phenylene-1',3'-phenylene-32-crown-10 在 三溴化磷 作用下， 以 乙醚 、 甲苯 为溶剂， 反应 18.0h， 以82%的产率得到17-(Bromomethyl)-2,5,8,11,14,20,23,26,29,32-decaoxatricyclo[31.3.1.115,19]octatriaconta-1(37),15(38),16,18,33,35-hexaene
  参考文献：
  名称：

  Syntheses of Monofunctional Derivatives of m-Phenylene-16-crown-5, Bis(m-phenylene)-32-crown-10, and m-Phenylene-p-phenylene-33-crown-10

  摘要：

  A series of monofunctional bis(m-phenylene)-32-crown-10 and m-phenylene-p-phenylene-33-crown-10 derivatives has been synthesized. Cyclization of m- and p-bis(omega-chlorotetraethyleneoxy)benzenes (6) with 5-substituted resorcinols 1 using pseudo-high dilution conditions in DMF and either CsF or K2CO3 as base afforded 5-carbomethoxy-1,3-phenylene-m-phenylene-32-crown-10 (7a, 46%), 5-carbomethoxy-1,3-phenylene-p-phenylene-33-crown-10 (7b, 48%), 5-(benzyloxy)-1,3-phenylen-m-phenylene-32-crown-10 (11b, 51%). Unsubstituted m-phenylene-p-phenylene-33-crown-10 (15) was also made (29%) in this way. Functional group conversions of the bis-phenylene macrocycles yielded 5-carboxy-1,3-phenylene-m-phenylene-32-crown-10 (8a), 5-(hydroxymethyl)-1,3-phenylene-m-phenylene-32-crawn-10 (9a), 5-(bromomethyl)-1,3-phenylene-m-phenylene-32-crown-10 (10a), 5-hydroxy-1,3-phenylene-m-phenylene-32-crown-10 (12a), 5-hydroxy-1,3-phenylene-p-phenylene-33-crown-10 (12b), 5-(phthalimidomethyl)-1,3-phenylene-m-phenylene-32-crown-10 (13a), and 5-(aminomethyl)-1,3-phenylene-m-phenylene-32-crown-10 (14a). Similarly 5-carbomethoxy-1,3-phenylene-16-crown-5 (4) was transformed to the corresponding acid (16), hydroxymethyl (17), formyl(18), bromomethyl (19), phthalimidomethyl (20), azidomethyl (21), and aminomethyl (22) derivatives. These compounds are building blocks for supramolecular assemblies (as shown by the synthesis of a Schiff base (23) from 18 and a diester (24) from 4,4'-biphenol and 17) and useful endcapping or pendant host components of macromolecules.

  DOI：

  10.1021/jo9619948
• 作为产物：
  描述：

  Methyl 2,5,8,11,14,20,23,26,29,32-decaoxatricyclo[31.3.1.115,19]octatriaconta-1(37),15(38),16,18,33,35-hexaene-17-carboxylate 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 反应 10.0h， 以90.5%的产率得到5-hydroxymethylene-1,3-phenylene-1',3'-phenylene-32-crown-10
  参考文献：
  名称：

  高通量溶液相合成的新方法：使用冠醚和铵离子相互作用进行亲和纯化

  摘要：

  描述了一种通过冠醚-铵离子相互作用亲和纯化合成化合物的新方法及其在几种肽和杂环的合成中的应用。通过以下步骤容易地从反应混合物中分离出具有冠醚（32-cro-10）部分的所需化合物。在每个反应循环之后，将反应混合物施加到氨基甲基化的聚苯乙烯柱（三氟乙酸形式）上。具有冠醚的化合物被选择性地吸附在色谱柱上，而没有冠醚的其他杂质（例如过量的试剂和副产物）被洗掉。随后被Et 3 N或CH 2 Cl 2解吸：MeOH（1∶1）得到所需的高纯度化合物。预期这种新策略将特别有用，特别是对于多个并行合成和组合库的准备。

  DOI：

  10.1016/s0040-4039(99)01507-5

文献信息

• Syntheses and Model Complexation Studies of Well-Defined Crown Terminated Polymers
  作者：Harry W. Gibson、Zhongxin Ge、Feihe Huang、Jason W. Jones、Hervé Lefebvre、Matthew J. Vergne、David M. Hercules

  DOI：10.1021/ma047811y

  日期：2005.4.1

  terminated polystyrenes of narrow molecular weight distribution (PDI). The DB24C8-terminated polymer 5 was demonstrated to form a pseudorotaxane complex (18) with dibenzylammonium hexafluorophosphate (17), but because of its small cavity, 5 cannot complex bulky N,N‘-dialkyl-4,4‘-bipyridinium (paraquat or viologen) salts. On the other hand, the BMP32C10-terminated polymer 11 complexed N,N‘-bis(p-tert-butylbenzyl)-4

  基于TEMPO-A自由基引发剂（4a中含有）二苯并-24-冠-8（DB24C8，图2a）部分的合成。类似的引发剂（图4b基于双）（米-亚苯基）-32-冠-10（BMP32C10，1B）还合成。基于冠的引发剂用于制备分子量分布窄（PDI）的冠醚封端的聚苯乙烯。已证明以DB24C8为末端的聚合物5与六氟磷酸二苄基铵（17）形成假轮烷络合物（18），但是由于其空腔小，所以5不能络合大体积的N，N。'-二烷基-4,4'-联吡啶鎓（百草枯或紫精）盐。在另一方面，所述BMP32C10封端的聚合物11络合N，N-双（p -叔丁基苄基）-4,4'-二吡啶鎓二（六氟磷酸盐（百草枯盐，23）强烈，但没有与相互作用六氟磷酸二苄（17）到可检测的程度。因此，这些新的聚合物主体是使用拟轮烷络合的超分子化学的大分子构建基，并且两者均显示出选择性。DB24C8聚合物对仲铵离子络合具有选择性，而BMP32C20聚合物对百
• A Supramolecular Triarm Star Polymer from a Homotritopic Tris(Crown Ether) Host and a Complementary Monotopic Paraquat-Terminated Polystyrene Guest by a Supramolecular Coupling Method
  作者：Feihe Huang、Devdatt S. Nagvekar、Carla Slebodnick、Harry W. Gibson

  DOI：10.1021/ja0438516

  日期：2005.1.1

  The first supramolecular star polymer based on pseudorotaxane host-guest complexation was prepared from statistical complexation of a homotritopic tris(crown ether) host and monotopic paraquat-terminated polystyrene guest in solution. The formation of this supramolecular star polymer was confirmed by proton NMR characterization and viscosity studies.
• Crowned Dendrimers:  pH-Responsive Pseudorotaxane Formation
  作者：Jason W. Jones、William S. Bryant、Anton W. Bosman、Rene A. J. Janssen、E. W. Meijer、Harry W. Gibson

  DOI：10.1021/jo0265784

  日期：2003.3.1

  With the end goal of incorporating the unique structural and physical properties of dendrimers into supramolecular assemblies, bis(m-phenylene)-32-crown-10-functionalized poly(propyleneimine) dendrimers of the first and third generations have been synthesized and their interaction with paraquat diol has been investigated. Using H-1 NMR, we determined that binding to the 4 or 16 crown ether sites occurred in an anti-cooperative fashion, most likely a result of steric influences. Upon protonation of the tertiary amines in the dendritic interior, binding became independent, i.e., statistical, and the average apparent association constant increased by nearly 5-fold; this effect is attributed to rigidification of the dendrimer, which makes its binding sites more accessible and less crowded.
• Syntheses of Monofunctional Derivatives of <i>m</i>-Phenylene-16-crown-5, Bis(<i>m</i>-phenylene)-32-crown-10, and <i>m</i>-Phenylene-<i>p</i>-phenylene-33-crown-10
  作者：Harry W. Gibson、Devdatt S. Nagvekar、Nori Yamaguchi、Feng Wang、William S. Bryant

  DOI：10.1021/jo9619948

  日期：1997.7.1

  A series of monofunctional bis(m-phenylene)-32-crown-10 and m-phenylene-p-phenylene-33-crown-10 derivatives has been synthesized. Cyclization of m- and p-bis(omega-chlorotetraethyleneoxy)benzenes (6) with 5-substituted resorcinols 1 using pseudo-high dilution conditions in DMF and either CsF or K2CO3 as base afforded 5-carbomethoxy-1,3-phenylene-m-phenylene-32-crown-10 (7a, 46%), 5-carbomethoxy-1,3-phenylene-p-phenylene-33-crown-10 (7b, 48%), 5-(benzyloxy)-1,3-phenylen-m-phenylene-32-crown-10 (11b, 51%). Unsubstituted m-phenylene-p-phenylene-33-crown-10 (15) was also made (29%) in this way. Functional group conversions of the bis-phenylene macrocycles yielded 5-carboxy-1,3-phenylene-m-phenylene-32-crown-10 (8a), 5-(hydroxymethyl)-1,3-phenylene-m-phenylene-32-crawn-10 (9a), 5-(bromomethyl)-1,3-phenylene-m-phenylene-32-crown-10 (10a), 5-hydroxy-1,3-phenylene-m-phenylene-32-crown-10 (12a), 5-hydroxy-1,3-phenylene-p-phenylene-33-crown-10 (12b), 5-(phthalimidomethyl)-1,3-phenylene-m-phenylene-32-crown-10 (13a), and 5-(aminomethyl)-1,3-phenylene-m-phenylene-32-crown-10 (14a). Similarly 5-carbomethoxy-1,3-phenylene-16-crown-5 (4) was transformed to the corresponding acid (16), hydroxymethyl (17), formyl(18), bromomethyl (19), phthalimidomethyl (20), azidomethyl (21), and aminomethyl (22) derivatives. These compounds are building blocks for supramolecular assemblies (as shown by the synthesis of a Schiff base (23) from 18 and a diester (24) from 4,4'-biphenol and 17) and useful endcapping or pendant host components of macromolecules.
• New methodology for high throughput solution-phase synthesis: affinity purification by using crown ether and ammonium ion interaction
  作者：San-qi Zhang、Koichi Fukase、Shoichi Kusumoto

  DOI：10.1016/s0040-4039(99)01507-5

  日期：1999.10

  (trifluoroacetic acid form). The compound possessing the crown ether was selectively adsorbed on the column, whereas other impurities without the crown ether such as excess reagents and byproducts were washed off. Subsequent desorption by Et3N or CH2Cl2:MeOH (1:1) afforded the desired compound with high purity. This new strategy is expected to be useful, for, in particular, multiple parallel synthesis and combinatorial

  描述了一种通过冠醚-铵离子相互作用亲和纯化合成化合物的新方法及其在几种肽和杂环的合成中的应用。通过以下步骤容易地从反应混合物中分离出具有冠醚（32-cro-10）部分的所需化合物。在每个反应循环之后，将反应混合物施加到氨基甲基化的聚苯乙烯柱（三氟乙酸形式）上。具有冠醚的化合物被选择性地吸附在色谱柱上，而没有冠醚的其他杂质（例如过量的试剂和副产物）被洗掉。随后被Et 3 N或CH 2 Cl 2解吸：MeOH（1∶1）得到所需的高纯度化合物。预期这种新策略将特别有用，特别是对于多个并行合成和组合库的准备。