16,17,19,20-tetramethyl-2,6,9,13-tetraaza[14]paracyclophane | 156753-62-7

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 16,17,19,20-tetramethyl-2,6,9,13-tetraaza[14]paracyclophane
• 英文别名: 17,18,19,20-Tetramethyl-3,7,10,14-tetrazabicyclo[14.2.2]icosa-1(18),16,19-triene
• CAS: 156753-62-7
• 化学式: C₂₀H₃₆N₄
• 分子量: 332.533
• InChiKey: RMMDNKQTYJSZSP-UHFFFAOYSA-N

物化性质

• 沸点：
  509.4±50.0 °C(predicted)
• 密度：
  0.916±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  24
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  48.1
• 氢给体数：
  4
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  4-氯甲基吡啶 、 16,17,19,20-tetramethyl-2,6,9,13-tetraaza[14]paracyclophane 在 zinc trifluoromethanesulfonate 、 potassium carbonate 作用下， 以 乙腈 为溶剂， 以34.2%的产率得到17,18,19,20-Tetramethyl-3-(pyridin-4-ylmethyl)-3,7,10,14-tetrazabicyclo[14.2.2]icosa-1(18),16,19-triene
  参考文献：
  名称：

  聚氮杂[n]对环芳烃的N-官能化中的显着选择性。N-（4-甲基吡啶基）取代的2,6,9,13-四氮杂[14]对环环烷烃的合成

  摘要：

  阳离子主体物种，特别是Zn 2+盐与聚氮杂[n]对环环烷（即2,6,9,13-四氮杂[14]对环环烷，B323（1a））的相互作用指导它们的选择性N-官能化。以这种方式，可以容易地获得在苄基氮原子上被ArCH 2-基单官能化或双官能化的化合物。通常，在不使用Zn 2+物种的情况下，与烷基化剂直接反应通常会生成非常复杂的单烷基化和多烷基化化合物的混合物，除非使用了4-吡啶甲基氯。在这种情况下，D323的单，二，三和四N-取代的衍生物可以根据所用烷基化剂的量来分离。在这种情况下，获得的单烷基化和二烷基化产物与使用金属辅助合成制备的产物不同。

  DOI：

  10.1016/s0040-4020(97)10075-8
• 作为产物：
  描述：

  3,6-双(溴甲基)-2,4,5-三甲基甲苯 在 disodium hydrogenphosphate 、 sodium amalgam 、 potassium carbonate 作用下， 以 四氢呋喃 、 甲醇 、 乙腈 为溶剂， 反应 72.0h， 生成 16,17,19,20-tetramethyl-2,6,9,13-tetraaza[14]paracyclophane
  参考文献：
  名称：

  An efficient synthesis of polyaza[n]paracyclophanes

  摘要：

  DOI：

  10.1021/jo00069a049

文献信息

• One-pot synthesis of polyaza[n]naphthalenophanes and polyaza[n]anthracenophanes
  作者：M.Isabel Burguete、Beatriu Escuder、Santiago V. Luis、Juan F. Miravet、Manuel Querol、Enrique García-España

  DOI：10.1016/s0040-4039(98)00587-5

  日期：1998.5

  Pernosylated polyaza[n]cyclophanes 13–20 were prepared by a Richman-Atkins modified methodology. Deprotection under mild conditions gave polyaza[n]cyclophanes 21–28. This methodology allows for the preparation of cyclophanes containing labile C-N bonds.

  用Richman-Atkins改良方法制备了Pernosylated的聚氮杂[n]环烷13-20。在温和的条件下脱保护得到聚氮杂[n] cyclophanes 21–28。该方法允许制备含有不稳定CN键的环烷。
• Selective monofunctionalization of polyaza[n]paracyclophanes
  作者：M.Isabel Burguete、Beatriz Escuder、Santiago V. Luis、Juan F. Miravet、Enrique García-España

  DOI：10.1016/0040-4039(94)88432-3

  日期：1994.11

  A new strategy to the preparation of selectively functionalized polyazamacrocycles is presented. Polyaza[n]paracyclophanes receptors are able to efficiently direct their own selective monofunctionalization upon interaction with simple guests such as metal cations. This enables the preparation of novel receptors functionalized at one of the benzylic nitrogen atoms with a variety of groups.

  提出了一种制备选择性官能化的聚氮杂大环化合物的新策略。聚氮杂[n]对环环烷酰胺受体能够在与简单的客人（例如金属阳离子）相互作用时有效地指导其自身的选择性单官能化。这使得能够制备在具有多个基团的苄基氮原子之一上官能化的新型受体。
• Guest-Induced Selective Functionalization of Polyaza[<i>n</i>]paracyclophanes
  作者：M. Isabel Burguete、Beatriu Escuder、Juan C. Frías、Enrique García-España、Santiago V. Luis、Juan F. Miravet

  DOI：10.1021/jo971329e

  日期：1998.3.1

  A new strategy to the preparation of selectively functionalized polyazamacrocycles is presented. Polyaza[n]paracyclophane receptors are able to efficiently direct their own selective functionalization upon interaction with simple guests such as metal cations. This enables the preparation of novel receptors functionalized at one of the benzylic nitrogen atoms with a variety of groups. Selective difunctionalization at both benzylic positions can also be achieved in this way.
• Burguete, M. Isabel; Garcia-Espana, Enrique; Luis, Santiago V., Chemical Communications, 1998, # 17, p. 1823 - 1824
  作者：Burguete, M. Isabel、Garcia-Espana, Enrique、Luis, Santiago V.、Miravet, Juan F.、Paya, Lorena、Querol, Manuel、Soriano, Conxa

  DOI：——

  日期：——
• Small Azaparacyclophanes as Potential Selective Scavengers of Mercury. Crystal Structure of the Complex Hg₂(<b>L1</b>)Cl₄ (<b>L1</b> = 16,17,19,20-Tetramethyl-2,6,9,13-tetraaza[14]paracyclophane)
  作者：Enrique García-España、Julio Latorre、Santiago V. Luis、Juan F. Miravet、Pedro E. Pozuelo、José A. Ramírez、Conxa Soriano

  DOI：10.1021/ic951615d

  日期：1996.1.1

  The ligational properties of the macrocycles 16,17,19,20-tetramethyl-2,6,9,13-tetraaza[14]paracyclophane (L1) and 2,6,9,13-tetraaza[ 14]paracyclophane (L2) and of its dibenzylated open-chain counterpart 1,12-dibenzyl-1,5,8,12-tetraazadodecane (L3) toward Hg2+ are reported. The equilibrium constants have been determined by potentiometry at 298.1 K in 0.15 mol dm(-3) NaCl. Competition of the ligands with chloride anions for the coordination of Hg2+ was required for the determination of the stability constants due to the high stability of the complexes formed. L1 and L2 selectively complex Hg2+ over first transition series metal ions and particularly over Cu2+. NMR measurements prove that just three of the four nitrogen donors in ligands L1 and L2 are involved in the coordination to Hg2+; the remaining benzylic nitrogen atom is not coordinated. NMR spectra also show a strong diamagnetic shielding (ca. 2 ppm) for one of the protons in the central methylene groups of the propylenic chain linked to the uncoordinated benzylic nitrogen. These signals appear for [HgL1](2+) at 0.3 ppm and for [HgL2](2+) at -0.4 ppm. The crystal structure of [Hg(2)L1Cl(4)] agrees with the NMR studies. Crystals of [Hg(2)L1Cl(4)] (C20H36Cl4Hg2N4) are monoclinic space group P2(1)/c, with n = 10.360(2) Angstrom, b = 17.535(2) Angstrom, c = 14.918(1) Angstrom, beta = 105.98(1)degrees, Z = 4, R(1) = 0.0471, wR(2) = 0.1064. The tetrahedral coordination polyhedra around the Hg2+ ions are formed in one case by the benzylic nitrogen atom and the two consecutive nitrogen atoms of the central part of the bridge and one chloride anion and, in the other case, by the remaining benzylic nitrogen and three chloride anions. Both coordination polyhedra are strongly distorted, particularly the one involving three nitrogen atoms of the bridge.