trans-calix[2]benzene[2]pyrrole

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: trans-calix[2]benzene[2]pyrrole
• 英文别名: 2,2,7,7,13,13,18,18-Octamethyl-24,26-diazapentacyclo[17.3.1.13,6.18,12.114,17]hexacosa-1(23),3,5,8(25),9,11,14,16,19,21-decaene；2,2,7,7,13,13,18,18-octamethyl-24,26-diazapentacyclo[17.3.1.13,6.18,12.114,17]hexacosa-1(23),3,5,8(25),9,11,14,16,19,21-decaene
• 化学式: C₃₂H₃₈N₂
• 分子量: 450.667
• InChiKey: LGEKKBSPAFWDTD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.9
• 重原子数：
  34
• 可旋转键数：
  0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  31.6
• 氢给体数：
  2
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  sodium trichloroacetate 、 trans-calix[2]benzene[2]pyrrole 以 乙二醇二甲醚 为溶剂， 反应 6.0h， 以36%的产率得到trans-calix[2]benzene[1]-3-chloropyridine[1]pyrrole
  参考文献：
  名称：

  Missing-Link Macrocycles: Hybrid Heterocalixarene Analogues Formed from Several Different Building Blocks

  摘要：

  The synthesis and structural characterization of hybrid heterocalix[4]arene analogues containing pyrrole, benzene, methoxy-substituted benzene, and pyridine subunits is described. Macrocycles I and 2, examples of calix[2]benzene[2]pyrrole and calix[I]benzene[3]pyrrole systems, respectively, are synthesized by the condensation of pyrrole and an appropriate pheny Ibis (carbinol). Macrocycles 3 and 7, examples of calix[2] benzene[ 1]pyridine [ 1]pyrrole and calix[1]pyridine[3]pyrrole, respectively, are synthesized by the use of a carbene-based pyrrole-to-pyridine ring-expansion procedure. Single-crystal X-ray analysis reveals that compounds la, 1b, and 2b adopt 1,3-alternate conformations in the solid state, whereas compounds 3 and 7 display structures that are best described as "flattened partial cones" in terms of their conformation. (Series a refers to pure benzene-derived systems, whereas series b indicates macrocycles containing 5-mothoxyphenyl subunits). In the solid state, the methoxy-functionalized macrocycles I b and 2b, and the chloropyridine-containing macrocycle 7 exist as dimers. In the case of la and 7, these compounds interact with neutral solvent in the solid state. The conformations of the macrocycles in solution were explored by temperature-dependent proton NMR and NOESY spectral analysis. At 188K, macrocycles I a and 2 a adopt flattened 1,3-alternate conformations, whereas macrocycles 3 and 7 exist in the form of flattened partial-cone conformations. Standard proton NMR titration analyses were carried out in the case of macrocycles I a and 2 a, and reveal that at least the second of these systems is capable of binding fluoride and chloride anions in CD,Cl, solution at room temperature (K-a = 571 and 17 M-1 in the case of 2 a and F- and Cl, respectively).

  DOI：

  10.1002/1521-3765(20020301)8:5<1134::aid-chem1134>3.0.co;2-m
• 作为产物：
  描述：

  吡咯 、 Α,Α'-二羟基-1,3-二异丙基苯 在 三氟化硼乙醚 作用下， 以 乙腈 为溶剂， 反应 1.0h， 以16%的产率得到trans-calix[2]benzene[2]pyrrole
  参考文献：
  名称：

  Missing-Link Macrocycles: Hybrid Heterocalixarene Analogues Formed from Several Different Building Blocks

  摘要：

  The synthesis and structural characterization of hybrid heterocalix[4]arene analogues containing pyrrole, benzene, methoxy-substituted benzene, and pyridine subunits is described. Macrocycles I and 2, examples of calix[2]benzene[2]pyrrole and calix[I]benzene[3]pyrrole systems, respectively, are synthesized by the condensation of pyrrole and an appropriate pheny Ibis (carbinol). Macrocycles 3 and 7, examples of calix[2] benzene[ 1]pyridine [ 1]pyrrole and calix[1]pyridine[3]pyrrole, respectively, are synthesized by the use of a carbene-based pyrrole-to-pyridine ring-expansion procedure. Single-crystal X-ray analysis reveals that compounds la, 1b, and 2b adopt 1,3-alternate conformations in the solid state, whereas compounds 3 and 7 display structures that are best described as "flattened partial cones" in terms of their conformation. (Series a refers to pure benzene-derived systems, whereas series b indicates macrocycles containing 5-mothoxyphenyl subunits). In the solid state, the methoxy-functionalized macrocycles I b and 2b, and the chloropyridine-containing macrocycle 7 exist as dimers. In the case of la and 7, these compounds interact with neutral solvent in the solid state. The conformations of the macrocycles in solution were explored by temperature-dependent proton NMR and NOESY spectral analysis. At 188K, macrocycles I a and 2 a adopt flattened 1,3-alternate conformations, whereas macrocycles 3 and 7 exist in the form of flattened partial-cone conformations. Standard proton NMR titration analyses were carried out in the case of macrocycles I a and 2 a, and reveal that at least the second of these systems is capable of binding fluoride and chloride anions in CD,Cl, solution at room temperature (K-a = 571 and 17 M-1 in the case of 2 a and F- and Cl, respectively).

  DOI：

  10.1002/1521-3765(20020301)8:5<1134::aid-chem1134>3.0.co;2-m

文献信息

• Switchable π-coordination and C–H metallation in small-cavity macrocyclic uranium and thorium complexes
  作者：Polly L. Arnold、Joy H. Farnaby、Rebecca C. White、Nikolas Kaltsoyannis、Michael G. Gardiner、Jason B. Love

  DOI：10.1039/c3sc52072b

  日期：——

  demonstrating the preference for arene binding by the electron-rich UIII ion. Facile loss of THF from [UI(THF)(L)] further increases the amount of U–arene back donation. [UI(L)] can incorporate a further UIII equivalent, UI3, to form the very unusual dinuclear complex [U2I4(L)] in which the single macrocycle adopts both κ5:κ5 and η6:κ1:η6:κ1 binding modes in the same complex. Hybrid density functional theory

  小腔，二吡咯化物，双阴离子大环反式杯[2]苯[2]吡咯化物（L）的新的，受构象限制的Th IV和U IV配合物[ThCl 2（L）]和[UI 2（L）] ）2-被报告，并示出为具有不寻常的κ 5：κ 5在弯曲金属茂型结构结合。[UI的单电子还原2（L）]，得到[UI（THF）（L）]并导致开关中配体的结合κ 5 -pyrrolide至η 6 -arene夹心配位，表明对于芳烃通过结合偏好富电子的U III离子。[UI（THF）（L）]中THF的少量损失进一步增加了U–arene返体捐赠的数量。[UI（L）]可以结合进一步ü III当量，UI 3，以形成非常不寻常的双核配合物[C 2我4（L）]，其中，单个大环化合物采用两个κ 5：κ 5和η 6：κ 1：η 6：κ 1结合在相同的复杂模式。进行了混合密度泛函理论计算，以比较[U III I（L）]和[U III 2 I 4（L）]表示[U 2
• Revealing the remarkable structural diversity of the alkali metal transfer agents of the trans-calix[2]benzene[2]pyrrolide ligand
  作者：M. Ángeles Fuentes、Antonio J. Martínez-Martínez、Alan R. Kennedy、Robert E. Mulvey

  DOI：10.1039/c6cc07240b

  日期：——

  Excellent reagents for transferring their heterocalix[4]arene ligand to f-block organometallic complexes, lithium, sodium and potassium trans-calix[2]benzene[2]pyrrolidides have been found to adopt a fascinating series of structures in their own right.

  已经发现出色的试剂可将其异杯形[4]芳烃配体转移至f嵌段有机金属络合物，锂，钠和钾反杯形[2]苯[2]吡咯烷化物本身具有引人入胜的结构。
• Samarium complexes of a σ-/π-pyrrolide/arene based macrocyclic ligand
  作者：Sougandi Ilango、Balamurugan Vidjayacoumar、Sandro Gambarotta

  DOI：10.1039/c002514n

  日期：——

  A bis-pyrrolide macrocyclic ligand [L = trans-calix[2]benzene[2]pyrrole(H)] containing two aromatic phenyl rings in the macrocycle backbone was reacted with SmCl3(THF)3 to afford the corresponding [LSmIIICl] (1) complex. Its crystal structure showed the ligand adopting the σ-bonding mode with the pyrrolide moieties and the π-bonding with the two aromatic rings. Reaction of 1 with MeLi in THF gave a

  一种 双吡咯化物 大环配体[L = 反式杯[2]苯[2]吡咯（H）使在大环主链中包含两个芳族苯环的]与 SmCl 3（四氢呋喃）3 负担相应的[LSM III Cl]（1）复杂。其晶体结构表明配体采用σ-键模式与吡咯化物部分和与两个芳环的π键。1与的反应梅里 在 四氢呋喃得到两种化合物的混合物。主要是由C–H活化的复合物[LSM III（四氢呋喃）]（2a）吡咯化物由于两个芳环之一的去质子化和金属化，环从σ-切换到π-。次要组成部分是不寻常的[（L）Sm III（HL'）]（2b）配合物，其既包含规则配体又包含“ N-混淆的”大环配体。两个配体将Sm中心包裹在常规配体上，并采用类似于1的键合模式。相反，第二个配体仅使用一个氮原子中的一个作为一个简单的σ键单齿配体吡咯化物戒指。但是，这个特殊的吡咯化物通过将环连接转移到大环上，N-部分已经异构化（N-混淆系统）。另外，第二吡咯化物环已在氮原子
• Thorium(IV) and Uranium(IV) <i>trans</i>-Calix[2]benzene[2]pyrrolide Alkyl and Alkynyl Complexes: Synthesis, Reactivity, and Electronic Structure
  作者：Markéta Suvova、Kieran T. P. O’Brien、Joy H. Farnaby、Jason B. Love、Nikolas Kaltsoyannis、Polly L. Arnold

  DOI：10.1021/acs.organomet.7b00633

  日期：2017.12.11

  The first thorium(IV) and uranium(IV) hydrocarbyl complexes of a trans-calix[2]benzene[2]pyrrolide macrocycle can use ligand noninnocence to enable multiple C–H bond activation reactions at the metal. Both alkyl and alkynyl complexes supported by the L dianion and L–2H tetraanion are reported. The ThIV and UIV monoalkyl-ate complexes [M(L–2H)An(R)] (M = K for R = CH2Ph, M = Li for R = Me, CH2SiMe3)

  反式杯[2]苯[2]吡咯化物大环的第一个or （IV）和铀（IV）烃基配合物可以利用配体无能使金属上的多个C–H键活化反应。由L二价阴离子和L支持的烷基和炔基络合物-2H报告tetraanion。Th IV和U IV单烷基化物配合物[M（L –2H）An（R）]（对于R = CH 2 Ph，M = K，对于R = Me，CH 2 SiMe 3，M = Li ），其中配体芳基被金属化，在整个金属和配体上添加末端炔烃的C–H键，形成An IV-炔基配合物[（L）An（C≡CR'）2 ]（R'= SiMe3，Si i Pr 3）。从（L该配体reprotonation -2H）4-至（L）2-伴随从η在配体的配位模式的变化5：η 1：η 5：η 1至η 5：η 5。另外，如果使用[Et 3 NH] [BPh 4 ]对配体进行质子化，则可以保留原始烷基，得到Th IV阳离子[（L）Th（R）] [BPh