O,O-双(二乙氧基磷酰基)杯[4]芳香烃 | 145237-28-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 酚类
• 中文名称: O,O-双(二乙氧基磷酰基)杯[4]芳香烃
• 英文名称: 25,27-bis-O-(diethoxyphosphoryl)calixarene
• 英文别名: 25,26-bis-O-(diethoxyphosphoryl)calix[4]arene；(27-Diethoxyphosphoryloxy-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) diethyl phosphate
• CAS: 145237-28-1
• 化学式: C₃₆H₄₂O₁₀P₂
• 分子量: 696.671
• InChiKey: DQTYOJDDYDYLOM-UHFFFAOYSA-N

物化性质

• 熔点：
  219-224°C
• 稳定性/保质期：

  遵照规定使用和储存，则不会分解。

计算性质

• 辛醇/水分配系数(LogP)：
  7.3
• 重原子数：
  48
• 可旋转键数：
  12
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  130
• 氢给体数：
  2
• 氢受体数：
  10

安全信息

• 储存条件：
  存储在阴凉干燥的地方。

反应信息

• 作为反应物：
  描述：

  O,O-双(二乙氧基磷酰基)杯[4]芳香烃 在 盐酸 、 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 以84%的产率得到
  参考文献：
  名称：

  Markovsky, Leonid N.; Visotsky, Miroslav A.; Pirozhenko, Vladimir V., Journal of the Chemical Society. Chemical communications, 1996, # 1, p. 69 - 72

  摘要：

  DOI：
• 作为产物：
  描述：

  4-叔丁基苯酚 在 aluminum (III) chloride 、 sodium hydride 作用下， 以 二苯醚 、 甲苯 为溶剂， 反应 20.0h， 生成 O,O-双(二乙氧基磷酰基)杯[4]芳香烃
  参考文献：
  名称：

  Phase Solubility Studies of Poorly Soluble Drug Molecules by Using O-Phosphorylated Calixarenes as Drug-Solubilizing Agents

  摘要：

  This study is the first report on the solubilizing effect of O-phosphorylated calix[n]arenes that form complexes with neutral molecules such as nifedipine, niclosamide, and furosemide by host-guest complexation. These complexation studies were carried out by using the phase solubility technique. From the obtained results, it was observed that the solubility of guest molecules such as nifedipine, niclosamide, and furosemide was significantly increased in the presence of host molecules tetrakis-O-(diethoxyphosphoryl)-p-tert-butylcalix[4]arene (1), tetrakis-O-(diethoxyphosphoryl)-calix[4]arene (2), bis-O-(diethoxyphosphoryl)-p-tert-butylcalix[4]arene (3), bis-O-(diethoxyphosphoryl)-calix[4]arene (4), and octakis-O-(diethoxyphosphoryl)-p-tert-butylcalix[8]arene (5). The increase in solubility of drugs by the calixarene host 1 to 5 was most probably due to inclusion complexation between drug molecules and cavities of the calixarene skeleton similar to drug-cyclodextrin complexes.

  DOI：

  10.1021/je200992c

文献信息

• Synthesis and Binding Properties of Phosphorus-Containing Calixarenes and Calixresorcinarenes
  作者：V.I. Kalchenko、M.A. Visotsky、A.N. Shivanyuk、V.V. Pirozhenko、L.N. Markovsky

  DOI：10.1080/10426509608545203

  日期：1996.1

  Abstract Full and regioselectively phosphorylated calix[4]arenes and calix[4]resorcinarenes were synthesized by Nickel catalyzed Arbuzov reaction of para-bromosubstituted calixarenes as well as by reaction of the hydroxyl-derivatives with chlorophosphates. Stereochemistry, chemical transformations, and complexation of the titled phosphorus-containing macrocycles were examined.

  摘要 通过镍催化的对位溴代杯芳烃的Arbuzov反应以及羟基衍生物与氯磷酸盐的反应，合成了完全和区域选择性磷酸化的杯[4]芳烃和杯[4]间苯二酚。检查了标题含磷大环的立体化学、化学转化和络合。
• <i>O</i>-Phosphorylated calix[4]arenes as Li⁺-selective­receptors
  作者：Oleg Lukin、Myroslav O. Vysotsky、Vitaly I. Kalchenko

  DOI：10.1002/poc.382

  日期：2001.7

  p-tert-butylcalix[4]arene 9 or calix[4]arene 10, having two diethoxyphosphoryl groups at distal positions on their narrow rim (phenolic oxygen atoms), by dibutyloxophosphinechloride or alkylation of 10 by methyl bromoacetate led to the corresponding tetrasubstituted calix[4]arenes 8b–d fixed in a cone conformation. The latter compounds and the similar derivative of calix[4]arene 8a with four diethoxyphosphoryl

  的磷酸化对-叔-butylcalix [4]芳烃9或杯[4]芳烃10，其在它们的窄边缘（酚氧原子）的远端位置处的两个二乙氧基磷酰基团，通过dibutyloxophosphinechloride或烷基化10通过导致相应的溴乙酸甲酯四取代杯[4]芳烃8b–d固定在圆锥构象中。后者的化合物和带有四个二乙氧基磷酰基的杯[4]亚芳烃8a的类似衍生物被发现具有锂阳离子选择性，这由碱金属苦味酸盐的THF溶液的UV-Vis光谱及其在水中的水-氯仿萃取所支持。配体8a–d的存在。已计算K / K选择性范围为2.9（8d）至9.5（8a），这是迄今为止报道的基于杯芳烃的Li +-选择性受体的最高值。版权所有©2001 John Wiley＆Sons，Ltd.
• Inherently Chiral Phosphoruscontaining Calix[4]Arenes
  作者：Leonid N. Markovsky、Miroslav A. Vysotsky、Maxim A. Tairov、Vitaly I. Kalchenko

  DOI：10.1080/10426509908546189

  日期：1999.1.1

  Inherently chiral phosphoruscontaining calix[4]arenes with asymmetrical placement of substituents at the macrocyclic lower rim (phenolic oxygen atoms) as well as with asymmetrical superposition of substituents at the upper rim (para-positions of benzene rings) and at the lower rim have been synthesized. The key steps of the synthesis are O,O-phosphorotropic rearrangements of 1,3-distally disubstituted

  固有的手性含磷杯[4]芳烃在大环下缘（酚氧原子）的取代基不对称放置以及上缘（苯环的对位）和下缘的取代基不对称叠加已被发现合成的。合成的关键步骤是由强碱诱导的 1,3- 远端双取代杯 [4] 芳烃的 O,O-磷向重排成 1,2- 近端异构体。
• Symmetrical and inherently chiral water-soluble calix[4]arenes bearing dihydroxyphosphoryl groups
  作者：Maxim A. Tairov、Myroslav O. Vysotsky、Olga I. Kalchenko、Vladimir V. Pirozhenko、Vitaly I. Kalchenko

  DOI：10.1039/b110691k

  日期：2002.5.23

  A series of symmetrical and inherently chiral water-soluble calix[4]arenes bearing one, two or four proton-ionisable dihydroxyphosphoryl groups at the narrow rim of the macrocycle has been synthesised by consecutive treatment of appropriate diethoxyphosphoryl derivatives with bromotrimethylsilane and methanol. The calix[4]arene phosphoric acids synthesised possess pKa-values 2.85–3.10 (CH3OH–H2O 70 : 30) and form salts with L-(−)-α-phenylethylamine or (1S,2R)-(+)-ephedrine in methanol solution. The salts of the inherently chiral calixarene phosphoric acids with chiral amines are easily separated into diastereomeric forms by the RP HPLC method on Separon SGX C18 or Partisil 5 ODS 3 achiral columns.

  通过用溴化三甲基硅烷和甲醇连续处理适当的二乙氧基磷衍生物，合成了一系列对称的、固有手性的水溶性钙[4]烯，这些钙[4]烯在大环的窄边上带有一个、两个或四个可质子离子化的二羟基磷基。合成的钙[4]炔磷酸的 pKa 值为 2.85-3.10（CH3OH-H2O 70：30），并在甲醇溶液中与 L-(-)-α-苯乙胺或 (1S,2R)-(+)-麻黄碱形成盐。在 Separon SGX C18 或 Partisil 5 ODS 3 非手性色谱柱上采用 RP HPLC 方法，可以轻松地将固有手性的钙烯烃磷酸盐与手性胺分离成非对映异构体。
• Transduction of selective recognition of heavy metal ions by chemically modified field effect transistors (CHEMFETs)
  作者：Peter L. H. M. Cobben、Richard J. M. Egberink、Johan G. Bomer、Piet Bergveld、Willem Verboom、David N. Reinhoudt

  DOI：10.1021/ja00052a063

  日期：1992.12

  Specifically substituted calix[4]arenes that complex selectively silver (2), copper (13), cadmium (23), and lead (29) cations were synthesized via di- and tetraalkylation of p-tert-butylcalix[4]arene. Calix[4]arenes derivatized with thioether, thioamide, and dithiocarbamoyl functionalities could be obtained in high overall yields. Integrated on a chemically modified field effect transistor (CHEMFET) the selective complexation of heavy metal ions by these calix[4]arenes is transduced directly into an electrical signal. An architecture for CHEMFETs is used in which a hydrophilic polyHEMA hydrogel is covalently attached between the gate oxide surface of a modified ISFET and the hydrophobic sensing membrane that contains the receptor molecule. CHEMFETs based on the calix[4]arene (2) with two diametrically substituted thioether functionalities responded selectively (60 mV decade-1) to a change in silver activity in the aqueous solution in the presence of potassium, calcium, cadmium, and copper ions (log K(ij) less-than-or-equal-to -4). The selectivity toward mercury (log K(ij) = -2.7) is comparable to the best neutral carrier based ISE so far. The calix[4]arene (13), with four dithiocarbamoyl groups, incorporated in a CHEMFET responsed Nernstian (30 mV decade-1) to a change in copper activity. The calix[4]arene (23), which has four dimethylthiocarbamoylmethoxyethoxy substituents, was selective in a CHEMFET (30 mV decade-1) toward cadmium in the presence of calcium and potassium ions. Two classes of ionophores can be distinguished for the selective detection of lead(II) cations by CHEMFETs, oxamide and thioamide ionophores, respectively. Tetrasubstitution of the calix[4]arene with thioamide groups (29) is a prerequisite for the selective detection of lead and leads to a highly selective CHEMFET (log K(ij) -3.4 to -5.2).