5,11,17,23-tetraacetyl-25,26,27,28-tetrahydroxycalix[4]arene | 109894-43-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 5,11,17,23-tetraacetyl-25,26,27,28-tetrahydroxycalix[4]arene
• 英文别名: 1-(11,17,23-Triacetyl-25,26,27,28-tetrahydroxy-5-pentacyclo[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-dodecaenyl)ethanone
• CAS: 109894-43-1
• 化学式: C₃₆H₃₂O₈
• 分子量: 592.645
• InChiKey: TWVMVXIWKBCJOM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5
• 重原子数：
  44
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  149
• 氢给体数：
  4
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  5,11,17,23-tetraacetyl-25,26,27,28-tetrahydroxycalix[4]arene 在 sodium azide 、 硫酸 作用下， 以 溶剂黄146 为溶剂， 以75%的产率得到5,11,17,23-tetraacetamido-25,26,27,28-tetrahydroxycalix<4>arene
  参考文献：
  名称：

  Morita, Yutaka; Agawa, Toshio; Kai, Yasushi, Chemistry Letters, 1989, p. 1349 - 1352

  摘要：

  DOI：
• 作为产物：
  描述：

  25,26,27,28-O-tetraacetylcalix[4]arene 在 三氯化铝 作用下， 以 硝基苯 为溶剂， 以93%的产率得到5,11,17,23-tetraacetyl-25,26,27,28-tetrahydroxycalix[4]arene
  参考文献：
  名称：

  Syntheses and NMR behavior of calix[4]quinone and calix[4]hydroquinone

  摘要：

  Calix[4]quinone (7) and calix[4]hydroquinone (6) have been synthesis using three different synthetic pathways. The first pathway to 7 from calix[4]arene (1) consists of six steps: acetylation, Fries rearrangement, Baeyer-Villiger oxidation after acetylation, hydrolysis, and oxidation. The second pathway to 7 from 1 consists of four steps: acetylation, Fries rearrangement, reaction of the product obtained by Fries rearrangement with sodium azide, and oxidation. The third pathway to 7 from 1 is most convenient and consists of three steps: diazo coupling reaction, reduction, and oxidation. The NMR behavior of 6 and 7 is described.

  DOI：

  10.1021/jo00039a027

文献信息

• Regioselective Friedel–Crafts acylation of calix[4]arenes
  作者：Jan Skácel、Jan Budka、Václav Eigner、Pavel Lhoták

  DOI：10.1016/j.tet.2015.02.021

  日期：2015.4

  Friedel–Crafts acylation of 25,27-dialkoxycalix[4]arenes has been studied. Direct acylation of de-tert-butylated calixarene using acyl chlorides and AlCl3 in 1,2-dichloroethane provided the corresponding diacyl derivatives regioselectively in high yields. Furthermore, ipso-substitution in the tert-butylated series under the same reaction conditions is possible, albeit in lower yields. As indicated

  研究了25,27-二烷氧基杯[4]芳烃的Friedel-Crafts酰化反应。在1,2-二氯乙烷中使用酰氯和AlCl 3对叔丁基化的杯芳烃进行直接酰化，可选择性地高产率提供相应的二酰基衍生物。此外，本位在3'-取代叔-butylated相同的反应条件下系列是可能的，尽管较低的产率。如该化学不成功应用到指示ø -酰基衍生物，所述本位杯的酰化反应[4]芳烃前进通过在上边缘直接攻击，而不是由一个Fries重排机制。
• Energy-Transfer Luminescence of Lanthanide Ions Encapsulated in Calix[4]arenes. Correlation between the Energy Level of Sensitizers and the Quantum Yield
  作者：Hitoshi Matsumoto、Seiji Shinkai

  DOI：10.1246/cl.1994.901

  日期：1994.5

  It was shown that the Tb3+ and Eu3+ complexes of 5,11,17,23-tetraacetyl-25,26,27,28-tetrakis(N,N-diethylaminocarbonylmethoxy)calix[4]arene give the high luminescence quantum yields (Φ = 0.164 for Tb3+ and 0.017 for Eu3+). The mechanistic investigations established that the high quantum yields are due to the energy level suitable to the energy-transfer and the presence of the carbonyl groups which mediate the intersystem crossing.

  研究表明，5,11,17,23-四乙酰基-25,26,27,28-四(N,N-二乙基氨基羰基甲氧基)钙[4]炔的 Tb3+ 和 Eu3+ 复合物具有很高的发光量子产率（Tb3+ 为 Φ = 0.164，Eu3+ 为 0.017）。机理研究表明，高量子产率得益于适合能量转移的能级以及介导系统间交叉的羰基的存在。
• Calixbenoquin: Calixarene-Based Cluster of Monobenzone as a New Anti-Tyrosinase Agent
  作者：Fazel Nasuhi Pur

  DOI：10.1007/s11094-022-02777-x

  日期：2022.12

  Tyrosinase, copper-containing glycoprotein, is a key enzyme in the biosynthesis of melanin pigment from L-tyrosine. The excessive production of melanin in the skin due to skin disorders, such as melasma, is of great importance. Therefore, tyrosinase inhibitors are used for treatments of them. One of these inhibitors is monobenzone (benoquin) as a skin whitening agent, which has a phenolic structure. The phenolic structure of this drug, prompted the author to design its novel calix[4]arene-based cluster in a chalice-shaped structure. Therefore, the present study reports the synthesis and in vitro anti-tyrosinase of the chalice-shaped cluster of benoquin (namely calixbenoquin) in comparison to its simple drug unit (benoquin) as the reference medication. The synthetic route included chemical modification of the calix[4]arene structure by grafting four hydroxyl and benzyloxy groups on the upper and the lower rim of the calix[4]arene scaffold, respectively. The in vitro biological results showed an enhanced (about 4.5-fold) anti-tyrosinase activity for the calixarene-based cluster (calixbenoquin) in relation to its phenolic monomer (benoquin). Therefore, compared to benoquin, calixbenoquin with improved bioactivity can be considered as a new melanogenesis inhibitor with low dose range. These improved pharmaceutical effects are probably attributed to the clustering effect and improved interaction of four impacted benoquin units of the cluster with the active site of tyrosinase.

  酪氨酸酶是一种含铜的糖蛋白，是从L-酪氨酸合成黑色素的关键酶。由于皮肤疾病（如黄褐斑）引起的皮肤中黑色素的过度产生非常重要。因此，酪氨酸酶抑制剂被用于治疗这些疾病。其中一种抑制剂是苯甲酮（苯甲醌），它是一种具有酚类结构的皮肤美白剂。这种药物的酚类结构促使作者设计了一种具有杯状结构的新型杯[4]芳烃基簇。因此，本研究报道了苯甲酮（即杯苯甲醌）的杯状簇的合成和体外抗酪氨酸酶活性，并将其与作为参考药物的简单药物单元（苯甲醌）进行了比较。合成路线包括对杯[4]芳烃结构进行化学修饰，分别在杯[4]芳烃支架的上缘和下缘上嫁接四个羟基和苄氧基。体外生物学结果表明，与酚类单体（苯甲醌）相比，基于杯芳烃的簇（杯苯甲醌）的抗酪氨酸酶活性增强（约4.5倍）。因此，与苯甲醌相比，具有更高生物活性的杯苯甲醌可被视为一种低剂量的新型黑色素生成抑制剂。这些药物效果的改善可能归因于簇效应以及簇中四个受影响的苯甲醌单元
• Huang, Zhi-Tang; Wang, Guo-Qiang, Chemische Berichte, 1994, vol. 127, # 3, p. 519 - 524
  作者：Huang, Zhi-Tang、Wang, Guo-Qiang

  DOI：——

  日期：——
• Morita, Yutaka; Agawa, Toshio; Kai, Yasushi, Chemistry Letters, 1989, p. 1349 - 1352
  作者：Morita, Yutaka、Agawa, Toshio、Kai, Yasushi、Kanehisa, Nobuko、Kasai, Nobutami、et al.

  DOI：——

  日期：——