4,11,18,25-tetrakis(carboxymethoxy)-3,5,7,10,12,14,17,19,21,24,26,28-dodecamethyl[1.1.1.1]metacyclophane | 145572-45-8

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 4,11,18,25-tetrakis(carboxymethoxy)-3,5,7,10,12,14,17,19,21,24,26,28-dodecamethyl[1.1.1.1]metacyclophane
• 英文别名: 2-[[11,17,23-Tris(carboxymethoxy)-4,6,10,12,16,18,22,24,25,26,27,28-dodecamethyl-5-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]oxy]acetic acid
• CAS: 145572-45-8
• 化学式: C₄₈H₅₆O₁₂
• 分子量: 824.965
• InChiKey: IDPQYUPNFHPXSQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.3
• 重原子数：
  60
• 可旋转键数：
  12
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  186
• 氢给体数：
  4
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  4,11,18,25-tetrakis(carboxymethoxy)-3,5,7,10,12,14,17,19,21,24,26,28-dodecamethyl[1.1.1.1]metacyclophane 在 氯化亚砜 、 三乙胺 作用下， 以 四氢呋喃 、 苯 为溶剂， 反应 12.0h， 生成 2-[[4,6,10,12,16,18,22,24,25,26,27,28-dodecamethyl-11,17,23-tris[2-oxo-2-[[(1S)-1-phenylethyl]amino]ethoxy]-5-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]oxy]-N-[(1S)-1-phenylethyl]acetamide
  参考文献：
  名称：

  Informational rigidity in mesitylene-based calix[4]arenes adopting a 1,3-alternate conformation

  摘要：

  Two chiral derivatives of a mesitylene-based calix[4]arene known to exist in the 1,3-alternate conformation were prepared by the attachment of homochiral residues to the four exo-hydroxy groups. Thus, the enantiotopic protons of the central scaffold became diastereotopic, leading to a doubling of their H-1 NMR signals in one example. From the temperature independence of the NR IR spectrum, a lower limit of 24.2 kcal/mol could be estimated for the barrier of ring inversion. MM3 calculations confirm the 1,3-alternate conformation as the energy minimum, and estimate a barrier of 25.7 kcal/mol for the 1,3-alternate-to-1,3-alternate* interconversion process. This high barrier is due to the repulsive steric interactions between exo-methyl groups at vicinal rings when these groups pass each other. (C), 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(00)00177-4
• 作为产物：
  描述：

  2,4,6-三甲酚 在 sodium hydroxide 、 四氯化锡 、 potassium carbonate 作用下， 以 1,4-二氧六环 、 乙醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 98.0h， 生成 4,11,18,25-tetrakis(carboxymethoxy)-3,5,7,10,12,14,17,19,21,24,26,28-dodecamethyl[1.1.1.1]metacyclophane
  参考文献：
  名称：

  Mesitylene-derived 1,3-alternate [1.1.1.1]metacyclophanes

  摘要：

  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.

  DOI：

  10.1021/jo00052a023

文献信息

• Covalently linked multi-calixarenes
  作者：O. Mogck、P. Parzuchowski、M. Nissinen、V. Böhmer、G. Rokicki、K. Rissanen

  DOI：10.1016/s0040-4020(98)00594-8

  日期：1998.8

  ipso-Nitration of t-butyl calix[4]arene tetraethers and subsequent hydrogenation provides an easy access to monoamino calix[4]arenes. Reaction with di- and triacid chlorides leads to various double- and triple-calix[4]arenes. With tetra-acid chlorides derived from calix[4]arenes in the cone- or 1,3-alternate-conformations penta-calix[4]arenes are available as molecularly uniform species, which may be regarded as the first generation of calix[4]arene based dendrimers. The structure of the mononitro tetraester derivative, which may serve as a general building block has been confirmed by single crystal X-ray analysis. (C) 1998 Elsevier Science Ltd. All rights reserved.
• 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.
• Informational rigidity in mesitylene-based calix[4]arenes adopting a 1,3-alternate conformation
  作者：Paweł Parzuchowski、Volker Böhmer、Silvio E Biali、Iris Thondorf

  DOI：10.1016/s0957-4166(00)00177-4

  日期：2000.6

  Two chiral derivatives of a mesitylene-based calix[4]arene known to exist in the 1,3-alternate conformation were prepared by the attachment of homochiral residues to the four exo-hydroxy groups. Thus, the enantiotopic protons of the central scaffold became diastereotopic, leading to a doubling of their H-1 NMR signals in one example. From the temperature independence of the NR IR spectrum, a lower limit of 24.2 kcal/mol could be estimated for the barrier of ring inversion. MM3 calculations confirm the 1,3-alternate conformation as the energy minimum, and estimate a barrier of 25.7 kcal/mol for the 1,3-alternate-to-1,3-alternate* interconversion process. This high barrier is due to the repulsive steric interactions between exo-methyl groups at vicinal rings when these groups pass each other. (C), 2000 Elsevier Science Ltd. All rights reserved.