4,11,18,25-tetrakis(chloromethyl)-3,5,7,10,12,14,17,19,21,24,26,28-dodecamethyl<1.1.1.1>metacyclophane | 145572-46-9

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: 4,11,18,25-tetrakis(chloromethyl)-3,5,7,10,12,14,17,19,21,24,26,28-dodecamethyl<1.1.1.1>metacyclophane
• 英文别名: 4,11,18,25-tetrakis(chloromethyl)-3,5,7,10,12,14,17,19,21,24,26,28-dodecamethyl[1.1.1.1]metacyclophane；4,11,18,25-tetra(chloromethyl)-3,5,7,10,12,14,17,19,21,24,26,28-dodecamethyl[1.1.1.1]metacyclophane；5,11,17,23-Tetrakis(chloromethyl)-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: 145572-46-9
• 化学式: C₄₄H₅₂Cl₄
• 分子量: 722.709
• InChiKey: DFWJCDQCYNJJDJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  13.6
• 重原子数：
  48
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.45
• 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：

  4,11,18,25-tetrakis(chloromethyl)-3,5,7,10,12,14,17,19,21,24,26,28-dodecamethyl<1.1.1.1>metacyclophane 在 potassium carbonate 、 溶剂黄146 作用下， 以 1,4-二氧六环 、 乙醇 为溶剂， 反应 44.0h， 生成 3,5,7,10,12,14,17,19,21,24,26,28-dodecamethyl<1.1.1.1>metacyclophane-4,11,18,25-tetramethanol
  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
• 作为产物：
  描述：

  2,4-双(氯甲基)三甲基苯 在 四氯化锡 作用下， 以 二硫化碳 为溶剂， 生成 4,11,18,25-tetrakis(chloromethyl)-3,5,7,10,12,14,17,19,21,24,26,28-dodecamethyl<1.1.1.1>metacyclophane
  参考文献：
  名称：

  SYNTHESIS, NMR AND X-RAY STRUCTURE OF PHOSPHORYLATED TETRAM ERIC METACYCLOPHANES

  摘要：

  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.

  DOI：

  10.1080/10426509908037020

文献信息

• Synthesis of four new carboxylic derivatives based on the [1.1.1.1]metacyclophane backbone blocked in 1,3-Alternate conformation
  作者：Ekaterina F. Chernova、Alexander S. Ovsyannikov、Sylvie Ferlay、Svetlana E. Solovieva、Igor S. Antipin、Alexander I. Konovalov、Nathalie Kyritsakas、Mir Wais Hosseini

  DOI：10.1016/j.tetlet.2018.02.060

  日期：2018.4

  Four new tetrasubstituted [1.1.1.1]metacyclophanes (4–7), that are inherently adopting a 1,3-Alternate conformation, bearing four or eight peripheral carboxylic binding sites, and appended with spacers group (alkyl or phenyl) differing by the flexibility, have been synthesised in high yields. The structures of the obtained compounds have been investigated in solution as well as in the solid state,

  四个新的四取代的[1.1.1.1] metacyclophanes（4 - 7），固有采用1,3-替代构象，轴承四个或八个外围羧酸结合位点，并用隔离物组（烷基或苯基）所附由灵活性不同，已经以高收率合成。通过使用单晶X射线分析，已经研究了其中三种溶液和固态形式的化合物的结构。
• Molecular tectonics: from a binuclear metallamacrocycle to a 1D isostructural coordination network based on tetracyanomethyl[1.1.1.1]metacyclophane and a silver cation
  作者：Ekaterina F. Chernova、Alexander S. Ovsyannikov、Sylvie Ferlay、Svetlana E. Solovieva、Igor S. Antipin、Alexander I. Konovalov、Nathalie Kyritsakas、Mir Wais Hosseini

  DOI：10.1016/j.mencom.2017.05.014

  日期：2017.5

  Depending on the anion (NO3- or BF4-) and stoichiometry, the combinations of [1.1.1.1]metacyclophane adopting a blocked 1,3-alternate conformation and bearing four cyanomethylene groups with silver cations under self-assembly conditions lead to the formation of either a 1D coordination network or a discrete binuclear metallomacrocycle.
• 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.