3,5,7,10,12,14,17,19,21,24,26,28-dodecamethyl [1.1.1.1]metacyclophane | 17623-16-4

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: 3,5,7,10,12,14,17,19,21,24,26,28-dodecamethyl [1.1.1.1]metacyclophane
• 英文别名: 3,5,7,10,12,14,17,19,21,24,26,28-dodecamethyl[1.1.1.1]metacyclophane；Cyclotetra-mesitylmesitylen；4,6,10,12,16,18,22,24,25,26,27,28-Dodecamethylcalix[4]arene；4,6,10,12,16,18,22,24,25,26,27,28-dodecamethylpentacyclo[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-dodecaene
• CAS: 17623-16-4
• 化学式: C₄₀H₄₈
• 分子量: 528.821
• InChiKey: LGEIYNNFQMAPMD-UHFFFAOYSA-N

物化性质

• 熔点：
  >300 °C
• 沸点：
  669.6±50.0 °C(Predicted)
• 密度：
  1.002±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  12.1
• 重原子数：
  40
• 可旋转键数：
  0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  3,5,7,10,12,14,17,19,21,24,26,28-dodecamethyl [1.1.1.1]metacyclophane 在 硫酸 、 硝酸 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 48.0h， 以81%的产率得到3,5,7,10,12,14,17,19,21,24,26,28-dodecamethyl-4,11,18,25-tetranitro[1.1.1.1]metacyclophane
  参考文献：
  名称：

  基于以 1,3-交替构象固定的均三甲苯衍生的 [1.1.1.1] Metacyclophane 外四齿配体的合成和固态结构分析

  摘要：

  获得了一系列基于固定在 1,3-交替构象中的 [1.1.1.1] 环芳烃骨架的新四齿配体。对于开发的策略，用于制备带有四个相互作用位点的十二个配体的通用合成子占据假四面体的顶点 [H, SH, CN, SCH3, CO2H, CHO, PPh2, P(O)Ph2, NO2, NH2 、吡啶和对甲氧基苯基]是四溴衍生物 7。除了适用于所有报道的配体的经典表征方法外，化合物 7、9、12 和 13 还在固态下通过单晶 X 射线进行结构研究衍射，这确实证实了它们的 1,3-交替构象。

  DOI：

  10.1002/1099-0690(200203)2002:5<802::aid-ejoc802>3.0.co;2-q
• 作为产物：
  描述：

  4,11,18,25-tetrabromo-3,5,7,10,12,14,17,19,21,24,26,28-dodecamethyl[1.1.1.1]metacyclophane 在 叔丁基锂 、 硫酸 、 水 作用下， 以 四氢呋喃 、 正戊烷 、 氯仿 为溶剂， 反应 0.5h， 以100%的产率得到3,5,7,10,12,14,17,19,21,24,26,28-dodecamethyl [1.1.1.1]metacyclophane
  参考文献：
  名称：

  基于以 1,3-交替构象固定的均三甲苯衍生的 [1.1.1.1] Metacyclophane 外四齿配体的合成和固态结构分析

  摘要：

  获得了一系列基于固定在 1,3-交替构象中的 [1.1.1.1] 环芳烃骨架的新四齿配体。对于开发的策略，用于制备带有四个相互作用位点的十二个配体的通用合成子占据假四面体的顶点 [H, SH, CN, SCH3, CO2H, CHO, PPh2, P(O)Ph2, NO2, NH2 、吡啶和对甲氧基苯基]是四溴衍生物 7。除了适用于所有报道的配体的经典表征方法外，化合物 7、9、12 和 13 还在固态下通过单晶 X 射线进行结构研究衍射，这确实证实了它们的 1,3-交替构象。

  DOI：

  10.1002/1099-0690(200203)2002:5<802::aid-ejoc802>3.0.co;2-q

文献信息

• Modular assembly of a preorganised, ditopic receptor for dicarboxylates
  作者：Maria H. Filby、Terry D. Humphries、David R. Turner、Ritu Kataky、Jaanus Kruusma、Jonathan W. Steed

  DOI：10.1039/b512779c

  日期：——

  Two types of calix[4]arene derived hosts for anions with, respectively, 1,3-alternate and cone conformations have been prepared; the 1,3-alternate system binds dicarboxylate anions in a ditopic manner while the cone compounds are deprotonated by carboxylates.

  我们制备了两种钙并[4]炔衍生的阴离子宿主，它们分别具有 1,3 邻位构象和锥形构象；1,3 邻位体系以二位方式结合二羧酸阴离子，而锥形化合物则被羧酸盐去质子化。
• Allosteric effects in a tetrapodal imidazolium-derived calix[4]arene anion receptor
  作者：Charlotte E. Willans、Kirsty M. Anderson、Lydia C. Potts、Jonathan W. Steed

  DOI：10.1039/b904148f

  日期：——

  1,3-alternate calix[4]arene host binds anions as 1 : 2 complexes via a range of CH⋯anion hydrogen bonds. Allosteric enhancement of the affinity for the second chloride anion is observed. X-Ray crystal structures of the chloride, bromide and nitrate complexes suggest that this behaviour is linked to inter-binding site communication mediated by the calixarene framework. The imidazolium groups exist as

  一种基于对位四足的咪唑鎓的1,3-替代物 杯[4]芳烃主体通过一系列CH阴离子氢键以1：2的配合物的形式结合阴离子。观察到对第二氯阴离子的亲和力的变构增强。氯化物，溴化物和硝酸盐络合物的X射线晶体结构表明，这种行为与杯芳烃骨架介导的相互结合位点通讯有关。咪唑鎓基团作为任一存在于出或出出构象异构体相对于所述杯芳烃，用氯化物络合物表现出构象同构，使得两种形式都存在于相同的晶体结构。
• Synthesis and characterization of a novel calix[4]arene tetramethyl tetraether
  作者：Tai Teh Wu、Judy R. Speas

  DOI：10.1021/jo00387a050

  日期：1987.5
• SYNTHESIS, NMR AND X-RAY STRUCTURE OF PHOSPHORYLATED TETRAM ERIC METACYCLOPHANES
  作者：Giuseppe A. Consiglio、Paolo Finocchiaro、Salvatore Failla、Ante Albert、Dietrich Mootz

  DOI：10.1080/10426509908037020

  日期：1999.1.1

  The synthesis of mesitylene-derived 1,3 alternate [1.1.1.1] metacyclophanes functionalized with pendant methylene-phosphonic acid diethyl ester groups is described. The compounds were fully characterized by H-1, C-13 and P-31-NMR spectra and by FAB-MS spectroscopy.The preferred conformation in solution was established by NMR methods, whereas the solid state conformation of one of them, solved by X-ray diffraction techniques, is also reported. The macrocycle forms a lattice clathrate with cyclohexane in the ratio 1:2 (macrocycle over guest) and alternates with an additional molecule of water in a hydrogen-bonded 1D array.
• Mesitylene-derived 1,3-alternate [1.1.1.1]metacyclophanes
  作者：Sebastiano Pappalardo、George Ferguson、John F. Gallagher

  DOI：10.1021/jo00052a023

  日期：1992.12

  Synthetic procedures to conformationally immobile 1,3-alternate [1.1.1.1]metacyclophanes based on mesitylene units are described. Coupling of mesitol (19) with bis(chloromethyl)mesitol (20) and bis(chloromethyl)mesitylene (21) in nitroethane in the presence of SnCl4 affords metacyclophanes 6 and 7-10, respectively, possessing extra-annular hydroxyl groups. Metacyclophanes 12 and 14, which hold one or two pairs of carboxyl groups in the distal positions, have been obtained from the appropriate distal diol 8 and tetrol 6 by treatment with tert-butyl bromoacetate followed by basic hydrolysis. Functionalized molecular frameworks, such as 15 and 18, have been also prepared in high yield by direct methods. The H-1 NMR spectral characteristics of 1,3-alternate metacyclophanes synthesized are briefly discussed. The structures of mono-, tri-, and tetrahydroxy metacyclophanes 10, 7, and 6, respectively, have been determined by X-ray crystallography. All three macrocycles have very similar 1,3-alternate-biconic conformations with approximate 42mBAR symmetry. Molecules 10 and 7 are isomorphous, and the lone hydroxyl group in 10 and the three hydroxyl groups in 7 are disordered over four possible sites. A toluene of solvation is docked against the molecular cavity in both 10 and 7. Compound 6 has crystallographic 2-fold symmetry and what would have been voids in the crystal lattice are occupied by disordered solvent molecules.