四(螺环己烷)杯(4)吡咯 | 35320-70-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 四吡咯及其衍生物
• 中文名称: 四(螺环己烷)杯(4)吡咯
• 英文名称: tetraspirocyclohexyl calix(4)pyrrole
• 英文别名: meso-tetracyclohexylcalix[4]pyrrole；tetrakis(spirocyclohexane)calix[4]pyrrole；meso-tetraspirocyclohexyl calix[4]pyrrole；Tetrakis(spirocyclohexane)calix(4)pyrrole
• CAS: 35320-70-8
• 化学式: C₄₀H₅₂N₄
• 分子量: 588.88
• InChiKey: LOTPVJIMYJUQPA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.8
• 重原子数：
  44
• 可旋转键数：
  0
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  63.2
• 氢给体数：
  4
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  四氢呋喃 、 四(螺环己烷)杯(4)吡咯 在 正丁基锂 作用下， 以 正己烷 为溶剂， 反应 2.0h， 生成 Li4(THF)4(tetrakis(cyclohexyl)porphyrinogenato)
  参考文献：
  名称：

  One- and Two-Electron Oxidative Pathways Leading to Cyclopropane-Containing Oxidized Porphyrinogens and C−C-Coupled Porphyrinogens from Alkali Cation− and Transition Metal−meso-Octaethylporphyrinogen Complexes

  摘要：

  This report deals with the different transition metal- and alkali cation-assisted oxidation pathways of the meso-octaethylporphyrinogen tetraanion [Et8N4](4-). The two-electron oxidation of [Et8N4Mn{Na(thf)(2)}(2)], 4, with Cp2FeBPh4 led to the corresponding monocyclopropane derivative [Et8N4(Delta)Mn], 6, [Delta = cyclopropane], while the one-electron oxidation with CuCl2 or O-2 led to the Mn(III)-porphyrinogen [Et8N4Mn][Li(thf)(4)], 5, which can be further oxidized by an excess of CuCl2 to [Et8N4(Delta)(2)Mn-Cl](+)[Cu9Cl11](0.5), 7. The formation of 7 does not follow the expected sequence Mn(II) --> Mn(III) --> Mn(II)-monocyclopropane --> Mn(II) - biscyclopropane-porphyrinogen. In the case of iron(II)-porphyrinogen, [Et8N4Fe{Li(thf)(2)}(2)], 9, the oxidation led in a preliminary stage to the iron(III) derivative [Et8N4Fe][Li(thf)(4)], 10, then to the metalated form of the biscyclopropane-porphyrinogen [Et8N4(Delta)(2)Fe-Cl]{mu-Cu4Cl5}], 11. The supposed stabilization of the biscyclopropane by the copper(I) cluster was ruled out by carrying the oxidation of [Cy4N4Fe{Li(thf)(2)}(2)], 11, to [Cy4N4(Delta)(2)Fe-Cl][Cu2Cl4], 14. The stepwise oxidation of [Et8N4M(thf)(4)] [M = Li, 1; M = Na, 2] with Cp2FeBPh4 led to [Et8N4(Delta)Li(2)thf(2)], 15, [Et8N4(Delta)Li]BPh4, 16, and [Et8N4(Delta)Na]BPh4, 17. The reaction of 1 with 16 leading to 15 showed how the C-C moiety in cyclopropane can be engaged in an intermolecular electron transfer. The reaction of 17 with 18-crown-6 allowed the release of biscyclopropane-porphyrinogen [Et8N4(Delta(2))] Particularly interesting is the thermal rearrangement of 15 to 19 occurring via intra- and intermolecular electron transfers with the transposition of the C-C bond of the cyclopropane to a C-C bridge across the beta position of two adjacent pyrroles. In the case of metals, such as Ni(II), which do not undergo oxidation state changes, the primary oxidation product of a metalla-meso-octaalkylporphyrinogen is the monocyclopropane derivative, which reacting with the starting material masks an overall one-electron oxidation. In fact, the reaction of [Et8N4Ni{Li(thf)(2)}(2)], 20, with 2 equiv of Cp2FeBPh4 led to the expected [Et8N4(Delta)Ni], 21, while the reaction of 20 with 1 equiv of Cp2FeBPh4 led to the dimer [(beta-beta)(Et8N4)(2)Ni-2], 22, which forms equally well from the reaction of 20 and 21. Complex 22 is a quite unique metallaporphyrinogen dimer, where the two monomeric units are joined via a C-C bond in the beta position of a pyrrole. Such a reaction shows that the methodology can accede to oligomeric forms of metallaporphyrinogens.

  DOI：

  10.1021/ja982178f
• 作为产物：
  描述：

  5,5'-cyclohexyldipyrromethane 在 甲烷磺酸 作用下， 以 甲醇 为溶剂， 反应 1.0h， 以46%的产率得到四(螺环己烷)杯(4)吡咯
  参考文献：
  名称：

  15α，20α-二（4-羟基苯基）杯[4]吡咯和10α，20β-二（4-羟基苯基）杯[4]吡咯的合成和晶体结构

  摘要：

  在甲磺酸作为催化剂的存在下，5,5'- dialkyldipyrromethanes与缩合反应p在甲醇羟基苯乙酮产生了意想不到的多取代15α的混合物，20α二（4-羟基苯基）杯[4]吡咯和预期的10α，20β-二（4-羟基苯基）杯[4]吡咯具有相对较低的产率。通过X射线衍射成功地确定了新杯[4]吡咯及其氧乙酸酯衍生物的晶体结构，并简要讨论了固态时的分子间相互作用。

  DOI：

  10.1016/j.tet.2013.10.036

文献信息

• Ytterbium(III) triflate catalyzed synthesis of calix[4]pyrroles in ionic liquids
  作者：Anil Kumar、Israr Ahmad、M Sudershan Rao

  DOI：10.1139/v08-121

  日期：2008.9.1

  Ytterbium(III) triflate has been utilized as a mild Lewis-acid catalyst for the synthesis of various calix[4]pyrroles by the condensation of pyrrole with different ketones in ionic liquids. The calix[4]pyrroles were obtained in high yield under ecofriendly, economical, and noncorrosive conditions, and the catalyst was recovered and recycled.Key words: calix[4]pyrrole, ionic liquid, ytterbium triflate.

  利用三酸镱作为温和的路易斯酸催化剂，在离子液体中通过吡咯与不同酮的缩合合成了各种钙并[4]吡咯。在环保、经济、无腐蚀的条件下，获得了高产率的钙并[4]吡咯，催化剂可回收再利用。
• Synthesis of a new calix[n]pyrrole: meso-pentaspirocyclohexyl calix[5]pyrrole
  作者：Mercedes Bedolla-Medrano、Luis Chacón-García、Claudia A. Contreras-Celedón、Jesús Campos-García

  DOI：10.1016/j.tetlet.2010.11.007

  日期：2011.1

  We describe the first synthesis of the novel meso-pentaspirocyclohexyl calix[5]pyrrole 2b. Anion–guest properties of the new compound were evaluated with respect to fluoride, chloride, and bromide tetrabutylammonium salts by 1H NMR titration techniques in deuterated dichloromethane at 22 °C by following the induced shifts in the NH resonances upon complexation.

  我们描述了新型的介孔五环环己基杯[5]吡咯2b的首次合成。通过1 H NMR滴定技术在氘化的二氯甲烷中于22°C下通过络合后NH共振的诱导位移，评估了该化合物相对于氟化物，氯化物和溴化物四丁基铵盐的阴离子-客体性能。
• Calix[4]pyrrolato Aluminates: The Effect of Ligand Modification on the Reactivity of Square‐Planar Aluminum Anions
  作者：Fabian Ebner、Philipp Mainik、Lutz Greb

  DOI：10.1002/chem.202005493

  日期：2021.3.17

  unusual oxidation or valence states. The recently reported methyl‐calix[4]pyrrolato aluminate established the effect of forcing a tetrahedral aluminum anion into a square‐planar coordination mode. However, the generality of this structural motif and any consequence of ligand modification remained open. Herein, a systematic ligand screening was launched, and the class of square‐planar aluminum anions was

  结构约束是一种有吸引力的工具，可以在不需要异常氧化或价态的情况下修改 p 区元素特性。最近报道的甲基杯[4]吡咯铝酸盐建立了迫使四面体铝阴离子进入方形平面配位模式的效应。然而，这种结构基序的普遍性和配体修饰的任何后果仍然是开放的。在此，启动了系统的配体筛选，并通过两种衍生物扩展了方形平面铝阴离子的类别，这两种衍生物在杯[4]吡咯配体处的内消旋取代方面有所不同。引人注目的是，这种修饰引发了对σ-供体的路易斯酸性结合模式与与羰基的铝配体合作结合模式的偏好的相反趋势。通过计算和键分析，可以深入了解这些违反直觉的实验观察的起源。重要的是，这一原理可能允许利用模式选择性结合来控制催化速率。
• N-Confused Calix[4]pyrroles
  作者：Stefaan Depraetere、Mario Smet、Wim Dehaen

  DOI：10.1002/(sici)1521-3773(19991115)38:22<3359::aid-anie3359>3.0.co;2-k

  日期：1999.11.15

  Next to the "normal" calix[4]pyrrole 1, the N-confused calix[4]pyrrole 2 is formed in substantial amounts (up to 22 % yield) as side product in the acid-catalyzed condensation reaction of ketones and pyrrole. In some cases, doubly N-confused calix[4]pyrroles are also formed.

  在酮和吡咯经酸催化的缩合反应中，副产物“正常”杯[4]吡咯1旁边大量生成了N缩合杯[4]吡咯2（产率高达22％）。在某些情况下，还会形成双氮键混合的杯[4]吡咯。
• Syntheses of Calix[4]Pyrroles by Amberlyst-15 Catalyzed Cyclocondensations of Pyrrole with Selected Ketones
  作者：Shive Chauhan、Bhaskar Garg、Tanuja Bisht

  DOI：10.3390/12112458

  日期：——

  A facile and efficient protocol is reported for the synthesis of calix[4]pyrrolesand N-confused calix[4]pyrroles in moderate to excellent yields by reaction of dialkyl orcycloalkyl ketones with pyrrole catalyzed by reusable AmberlystTM-15 under eco-friendlyconditions.

  报道了一种简便高效的合成方法，用于在生态友好的条件下，通过可重复使用的AmberlystTM-15催化下，将二烷基或环烷基酮与吡咯反应，合成卡利克斯[4]吡咯和N混淆卡利克斯[4]吡咯，产率适中至优良。