5-formyl-25,27-dipropoxy-26,28-dihydroxycalix[4]arene | 216525-38-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 5-formyl-25,27-dipropoxy-26,28-dihydroxycalix[4]arene
• 英文别名: 26,28-dihydroxy-25,27-dipropoxycalix[4]arene-5-carbaldehyde；26,28-Dihydroxy-25,27-dipropoxypentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(24),3,5,7(28),9,11,13(27),15(26),16,18,21(25),22-dodecaene-5-carbaldehyde
• CAS: 216525-38-1
• 化学式: C₃₅H₃₆O₅
• 分子量: 536.668
• InChiKey: NJLBQAITWCLNMF-UHFFFAOYSA-N

物化性质

• 沸点：
  708.8±60.0 °C(Predicted)
• 密度：
  1.180±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  8.2
• 重原子数：
  40
• 可旋转键数：
  7
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  76
• 氢给体数：
  2
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  5-formyl-25,27-dipropoxy-26,28-dihydroxycalix[4]arene 在 盐酸 、 三甲基溴硅烷 作用下， 以 1,4-二氧六环 、 氯仿 为溶剂， 反应 51.5h， 生成 26,28-dihydroxy-25,27-dipropoxycalix[4]arene-5-(α-hydroxymethylphosphonic acid)
  参考文献：
  名称：

  杯[4]芳烃-α-羟基膦酸。谷胱甘肽S-转移酶的合成、立体化学和抑制

  摘要：

  通过相应的单-和二-甲酰基杯芳烃与二烷基钠盐的反应，制备了一系列在大环上缘带有一个或两个α-羟甲基膦酸片段的二丙氧基-、三丙氧基-和四丙氧基杯（4）芳烃。亚磷酸酯或与三烷基（三甲基甲硅烷基）亚磷酸酯，然后酯衍生物的脱烷基化（脱甲硅烷基化）。通过 1 H NMR研究了大环骨架的构象和所得化合物的立体异构形式。发现所得的α-羟甲基膦酸能够在体外抑制谷胱甘肽S-转移酶的活性。

  DOI：

  10.3998/ark.5550190.0013.421
• 作为产物：
  描述：

  1,1-二氯甲醚 、 25,27-dihydroxy-26,28-dipropoxycalix[4]arene 在 四氯化钛 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以95%的产率得到5-formyl-25,27-dipropoxy-26,28-dihydroxycalix[4]arene
  参考文献：
  名称：

  Arimura, Takashi; Ide, Seiji; Nishioka, Takuya, Journal of Chemical Research - Part S, 2000, # 5, p. 234 - 236

  摘要：

  DOI：

文献信息

• Calix[4]arenes bearing?-amino- or?-hydroxyphosphonic acid fragments at the upper rim
  作者：Andrew Solovyov、Sergey Cherenok、Ivan Tsymbal、Salvatore Failla、Giuseppe A. Consiglio、Paolo Finocchiaro、Vitaly Kalchenko

  DOI：10.1002/hc.2

  日期：——

  esters of calix[4]arenes 7, 10, 18, and 21 with bromotrimethylsilane and methanol gave dihydroxyphosphoryl derivatives of calix[4]arenes 24–27. It was shown that calix[4]arenes bearing at the macrocyclic upper rim hydroxymethylphosphonic fragments, as well as bis-hydroxymethyl(aminomethyl)phosphonic fragments, are able to undergo self-assembly with formation of dimeric OH···O=P hydrogen bonded associates

  通过对甲酰基杯[4]芳烃1-6与亚磷酸三烷基酯在干燥氯化氢存在下反应，合成了在上缘具有二烷基磷酰基-羟甲基基团的杯[4]芳烃7-13。用二烷基磷酰基-烷基（芳基）氨基甲基官能化的杯[4]芳烃 18-23 通过钠促进的亚磷酸二烷基酯加成到对亚氨基杯 [4] 芳烃 14-17 的 C=N 键获得。用溴代三甲基硅烷和甲醇连续处理杯 [4] 芳烃 7、10、18 和 21 的 α-羟基-或 α-氨基膦酸二烷基酯，得到杯 [4] 芳烃 24-27 的二羟基磷酰基衍生物。结果表明，杯[4]芳烃在大环上缘带有羟甲基膦酸片段，以及双羟甲基（氨甲基）膦酸片段，能够进行自组装，形成二聚 OH···O=P 氢键缔合物。© 2001 John Wiley & Sons, Inc. 杂原子化学 12:58–67, 2001
• Calix[4]arene methylenebisphosphonic acids as calf intestine alkaline phosphatase inhibitors
  作者：Andriy I. Vovk、Vitaly I. Kalchenko、Sergey A. Cherenok、Valery P. Kukhar、Oxana V. Muzychka、Myron O. Lozynsky

  DOI：10.1039/b409526j

  日期：——

  Calix[4]arenes bearing one or two methylenebisphosphonic acid fragments were prepared via addition of diethylphosphite to the parent calix[4]arene aldehydes. The resulting compounds displayed stronger inhibition of calf intestine alkaline phosphatase than simple methylenebisphosphonic or 4-hydroxyphenyl methylenebisphosphonic acids. The action of these phosphorylated calix[4]arenes is concordant with partial mixed-type inhibition. The inhibition constants Ki and Ki′ for the calix[4]arene bis(methylenebisphosphonic) acid in Tris-HCl buffer at pH 9 are 0.38 µM and 2.8 µM respectively. The replacement of the phosphoric acid moieties on the macrocycle with diethylphosphonates results in a sharp decrease of its inhibitory action. Preorganizing phosphonic acid fragments using a calixarene platform therefore provides a promising approach for the design of efficient alkaline phosphatase inhibitors.

  通过在母体钙[4]烯醛中加入亚磷酸二乙酯，制备出含有一个或两个亚甲基二膦酸片段的钙[4]烯醛。与单纯的亚甲基二膦酸或 4-羟基苯基亚甲基二膦酸相比，所制备的化合物对小牛肠道碱性磷酸酶的抑制作用更强。这些磷酸化钙[4]烯的作用与部分混合型抑制作用一致。在 pH 值为 9 的 Tris-HCl 缓冲液中，钙[4]炔双亚甲基二膦酸的抑制常数 Ki 和 Ki′分别为 0.38 µM 和 2.8 µM。用二乙基膦酸盐取代大环上的磷酸分子会导致其抑制作用急剧下降。因此，利用钙杂蒽平台预组织膦酸片段为设计高效的碱性磷酸酶抑制剂提供了一种前景广阔的方法。
• Complexation of calix[4]arenehydroxymethylphosphonic acids with amino acids. Binding constants determination of the complexes by HPLC method
  作者：Olga Kalchenko、Sergiy Cherenok、Olexander Yushchenko、Vitaly Kalchenko

  DOI：10.1007/s10847-012-0169-x

  日期：2013.6

  Host–Guest complexation process of calixarenehydroxymethylphosphonic acids with 10 amino acids in solution H2O/MeCN (99:1) had been studied. Binding constants of the inclusion complexes from the dependence between capacity factors of the Guest and the calixarene-Host concentration in the mobile phase had been calculated. It was shown the binding constants depend on the nature of the amino acid residue, conformation of the calixarene skeleton, quantity of phosphoryl groups at the upper rim. In accordance with molecular calculation the complexation is determined by the electrostatic interactions between the positively charged nitrogen atom of amino acid and the negatively charged oxygen atom of phosphonic group of calixarene molecule, hydrogen bonds, π–π, CH–π and solvatophobic, interactions.

  研究了在 H2O/MeCN 溶液（99:1）中卡利沙雷因羟甲基膦酸与 10 种氨基酸的主客体络合过程。根据客体的容量因子与流动相中钙沙雷因-客体浓度之间的关系，计算出了包合物的结合常数。结果表明，结合常数取决于氨基酸残基的性质、卡利卡林骨架的构象以及上缘磷酰基团的数量。根据分子计算结果，氨基酸带正电荷的氮原子与钙铝烯烃分子带负电荷的膦基氧原子之间的静电作用、氢键、π-π、CH-π 和疏溶作用决定了复合物。
• Synthesis of Calixarene-Methylenebisphosphonic Acids and Their Influence on Fibrin Polymerization
  作者：S. O. Cherenok、O. A. Yuschenko、P. G. Gritsenko、E. V. Lugovskoy、T. A. Koshel、V. I. Chernishov、I. O. Koliesnik、O. I. Kalchenko、S. V. Komisarenko、V. I. Kalchenko

  DOI：10.1080/10426507.2010.521212

  日期：2011.3.31

  A series of hydroxycalix[4]arenes bearing one, two, or four fragments of methylenebisphosphonic acids was synthesized by the reaction of appropriate formylcalixarenes with sodium salts of dialkylphosphites. These calixarenes inhibit specifically 50% of fibrin polymerization in the fibrinogen + thrombin reaction as well as monomeric fibrin desAABB polymerization in concentration up to 0.5 x 10(-6) M.
• Synthesis of calixarene-based ketocyanine fluorophores
  作者：Yuriy Matvieiev、Iuliia Karpenko、Andrii Kulinich、Aleksey Ryabitskii、Vasyl Pivovarenko、Svitlana Shishkina、Oleg Shishkin、Vitaly Kalchenko

  DOI：10.1016/j.tetlet.2011.05.094

  日期：2011.7

  Cup-shaped calix[4]arenes bearing one or two ketocyanine fluorophore fragments at the wide rim of the macrocycle are synthesized by condensation of formyl calix[4]arenes with arylmethylene(hetarylmethylene)cyclopentanones in the presence of the ionic liquid, dimethylammonium dimethylcarbamate (DIMCARB) and characterized using UV-vis and fluorescence spectroscopy. Strong positive solvatofluorochromism for the calixarene ketocyanines is observed. (C) 2011 Elsevier Ltd. All rights reserved.