5,17-dibromo-11,23-bis(diphenylphosphino)-25,26,27,28-tetra-n-propoxycalix[4]arene | 392743-35-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 5,17-dibromo-11,23-bis(diphenylphosphino)-25,26,27,28-tetra-n-propoxycalix[4]arene
• 英文别名: 5,17-dibromo-11,23-bis(diphenylphosphino)-25,26,27,28-tetrapropoxycalix[4]arene；5,17-dibromo-11,23-diphenylphosphino-25,26,27,28-tetra-n-propoxycalix[4]arene；(11,23-Dibromo-17-diphenylphosphanyl-25,26,27,28-tetrapropoxy-5-pentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(24),3,5,7(28),9,11,13(27),15(26),16,18,21(25),22-dodecaenyl)-diphenylphosphane
• CAS: 392743-35-0
• 化学式: C₆₄H₆₄Br₂O₄P₂
• 分子量: 1118.97
• InChiKey: BUSMZRKNNPGNNP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  17.9
• 重原子数：
  72
• 可旋转键数：
  18
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  5,17-dibromo-11,23-bis(diphenylphosphino)-25,26,27,28-tetra-n-propoxycalix[4]arene 在 palladium diacetate 、 1,2-二溴乙烷 、 sodium hydroxide 作用下， 以 水 、 1,2-二氯乙烷 为溶剂， 反应 7.0h， 以71%的产率得到5-diphenylphosphino-17-diphenylphosphinoyl-25,26,27,28-tetrapropoxycalix[4]arene
  参考文献：
  名称：

  Calixarene-monophosphines as supramolecular chelators

  摘要：

  合成了多种具有二苯基膦基团的钙木[4]芳烃，结构为5-二苯基膦基-17-R1-11,23-二R2-25,26,27,28-四丙氧基钙木[4]芳烃（1, R1 = R2 = Br；2, R1 = Br, R2 = H；3, R1 = R2 = 对甲基苯基；4, R1 = 对甲基苯基, R2 = H；5, R1 = R2 = H；20, R1 = 对甲基苯基, R2 = H），这些化合物是从5,11,17,23-四溴-25,26,27,28-四丙氧基钙木[4]芳烃出发合成的。1-5与[RuCl2(p-cymene)]2的反应定量生成了单膦配合物[RuCl2(p-cymene)L]，其中内向的钌原子单元位于由四个酚氧基环界定的锥体内部。P–Ru矢量的特定取向似乎是由p-茨烯配体与两个芳香腔壁之间的π–π相互作用所造成的。总体而言，在每种情况下，配体的钙木芳烃末端表现出对Ru(p-cymene)片段的超分子识别能力。在顺式-[PtCl2·12]和[RuCl2(p-cymene)·20]配合物中观察到了与外向P–M键形成的现象。通过对[RuCl2(p-cymene)·3]进行的变温研究显示，钌被嵌入一个扩展的锥体中，p-茨烯环围绕Ru-芳香环键发生快速振荡，这种振荡可以在低温下被冻结。[RuCl2(p-cymene)·3]与AgBF4在CH3CN中的反应导致腔内反应，其中一个氯配体被乙腈取代。

  DOI：

  10.1039/b907100h
• 作为产物：
  描述：

  25,26,27,28-tetrapropyloxycalix[4]arene 在 N-溴代丁二酰亚胺(NBS) 、 正丁基锂 作用下， 以 四氢呋喃 、 丁酮 为溶剂， 生成 5,17-dibromo-11,23-bis(diphenylphosphino)-25,26,27,28-tetra-n-propoxycalix[4]arene
  参考文献：
  名称：

  Regioselective upper-rim functionalizations of calix[4]arene by diphenylphosphino groups

  摘要：

  对calix[4]arene的上缘选择性官能化已经进行，以制备所有多取代二苯基膦衍生物。此外，已确定了5,17-二溴-11,23-双(二苯基膦基)-25,26,27,28-四-n-丙氧基calix[4]arene和5,11,17,23-四(二苯基膦基)-25,26,27,28-四异丙氧基calix[4]arene的X射线结构。通过适当选择碱、烷基锂-溶剂系统、化学计量、反应时间等方法实现了选择性官能化。开发了一种新的便捷方法，可在相对较大规模上选择性地制备calix[4]arenes的衍生物，涉及将远端二酯衍生物转酯化为近端异构体。关键词：calix[4]arenes、膦、上缘、X射线结构、转酯化。

  DOI：

  10.1139/v01-161

文献信息

• Positioning of transition metal centres at the upper rim of cone-shaped calix[4]arenes. Filling the basket with an organometallic ruthenium unit
  作者：Manuel Lejeune、Catherine Jeunesse、Dominique Matt、Nathalie Kyritsakas、Richard Welter、Jean-Pierre Kintzinger

  DOI：10.1039/b110884k

  日期：2002.4.9

  A series of calix[4]arenes bearing diphenylphosphino groups tethered at the upper rim have been prepared by treatment of 5,11,17,23-tetrabromo-25,26,27,28-tetrapropoxycalix[4]arene with ButLi (or BunLi) followed by reaction with PPh2Cl. The tetraphosphinated derivative 3 was found suitable for the formation of tetranuclear species, notably [3·(AuCl)4], [3·RuCl2(p-cymene)}4], and [3·PdCl(o-C6H4CH2NMe2)}4], all possessing an apparent C4v-symmetry in solution. Reaction of [RuCl2(p-cymene)]2 with the diphosphines 5,17-di-X-11,23-bis(diphenylphosphino)-25,26,27,28-tetrapropoxycalix[4]arene (X = H, 1; X = Br, 4) afforded the C2v-symmetrical dinuclear complexes [1·RuCl2(p-cymene)}2] and [4·RuCl2(p-cymene)}2], respectively. Reaction of the non-brominated diphosphine 1 with [PdCl(o-C6H4CH2NMe2)]2 gave the complex [1·PdCl(o-C6H4CH2NMe2)}2]. Reaction at high dilution of [PtCl2(1,5-cyclooctadiene)] with 4 or 1 resulted in quantitative formation of the corresponding cis-chelate complexes [4·PtCl2] (12) and [1·PtCl2] (13), respectively. The trans version of 13 could also be obtained, provided that [PtCl2(PhCN)2] was used as starting complex. In the solid state, the PtCl2 unit of 12 is directed towards one bromine atom, resulting in a highly unsymmetrical calixarene structure where the metal plane is nearly parallel to the calix reference plane. The NMR spectra of 12 and 13 show an apparent C2v-symmetrical structure, suggesting a fast fan-like motion in solution of the metal plane about the P⋯P axis. Similar dynamics are likely to occur in the related cationic complexes [1·Rh(norbornadiene)]BF4 (15) and [1·Pd(Me-allyl)]BF4 (16). As shown by variable temperature studies carried out on 12 and 16, these dynamics couple with a concomitant, restricted rotation of the two PPh2 units about their coordination axis. The latter motion is probably a result of steric interactions within the phosphorus environment, two PPh rings being in competition for occupation of the cavity entrance. Reaction of the expanded cavity 5,11,17-tribromo-23-diphenylphosphino-25,26,27,28-tetrapropoxycalix[4]arene 5 with [RuCl2(p-cymene)]2 afforded the monophosphine complex [5·RuCl2(p-cymene)]. In solution as well in the solid state, the p-cymene ligand fills the calixarene basket.

  通过用 ButLi（或 BunLi）处理 5,11,17,23-四溴-25,26,27,28-四丙氧基杯[4]芳烃，制备了一系列在上缘带有二苯基膦基团的杯[4]芳烃。 ），然后与 PPh2Cl 反应。发现四膦化衍生物 3 适合形成四核物质，特别是 [3·(AuCl)4]、[3·RuCl2(p-cymene)}4] 和 [3·PdCl(o-C6H4CH2NMe2)} 4]，在溶液中均具有明显的 C4v 对称性。 [RuCl2(p-伞花烯)]2 与二膦 5,17-二-X-11,23-双(二苯基膦)-25,26,27,28-四丙氧基杯[4]芳烃的反应 (X = H, 1; X = Br, 4) 分别得到C2v对称双核配合物[1·RuCl2(对伞花烃)}2]和[4·RuCl2(对伞花烃)}2]。非溴化二膦1与[PdCl(o-C6H4CH2NMe2)]2反应得到络合物[1·PdCl(o-C6H4CH2NMe2)}2]。高稀释度的 [PtCl2(1,5-环辛二烯)] 与 4 或 1 发生反应，定量形成相应的顺式螯合物 分别为配合物[4·PtCl2] (12) 和[1·PtCl2] (13)。如果使用[PtCl2(PhCN)2]作为起始复合物，也可以获得13的反式版本。在固态下，12 的 PtCl2 单元指向一个溴原子，形成高度不对称的杯芳烃结构，其中金属平面几乎平行于杯参考平面。 12 和 13 的 NMR 谱显示出明显的 C2v 对称结构，表明金属平面溶液中围绕 P⋯P 轴的快速扇形运动。类似的动态也可能发生 发生在相关的阳离子配合物 [1·Rh(降冰片二烯)]BF4 (15) 和 [1·Pd(Me-烯丙基)]BF4 (16) 中。正如对 12 和 16 进行的变温研究所示，这些动力学与两个 PPh2 单元绕其协调轴的伴随的、受限的旋转耦合。后一种运动可能是磷环境内空间相互作用的结果，两个 PPh 环竞争占据空腔入口。膨胀空腔 5,11,17-三溴-23-二苯基膦-25,26,27,28-四丙氧基杯[4]芳烃 5 与 [RuCl2(对伞花烃)]2 反应得到单膦配合物 [5·RuCl2(对伞花烃）]。在溶液中以及在固态中，对伞花烯配体填充杯芳烃篮。
• Syntheses and Characterization of Upper Rim 1,2- and 1,3-Diphosphinated Calix[4]arenes and Their Corresponding 1,5-Cyclooctadienylrhodium(I) Complexes:  Comparison of the Catalytic Hydroformylation Properties of Terminal Alkenes
  作者：François Plourde、Karine Gilbert、Jonathan Gagnon、Pierre D. Harvey

  DOI：10.1021/om030095o

  日期：2003.7.1

  28-tetra-n-propoxycalix[4]arene (1,3-isomer) ligands (alkyl = Me, i-Pr) have been prepared and coordinated to Rh(COD)+ fragments (COD = 1,5-cyclooctadiene). The ligands 5,17-bis(diphenylphosphino)-11,23-dibromo-25,26,27,28-tetra-n-propoxycalix[4]arene and 5,11-bis(diphenylphosphino)-25,26,27,28-tetra-n-propoxycalix[4]arene have been coordinated to M(COD)+ (M = Rh, Ir) and RhCl(CO) fragments, as well. On the basis of

  5,11-（1,2-异构体）和5,17-双（二烷基膦基）-25,26,27,28-四正丙氧基杯[4]芳烃（1,3-异构体）配体（烷基=已制备Me，i- Pr）并与Rh（COD）+片段配位（COD = 1,5-环辛二烯）。配体5,17-双（二苯基膦基）-11,23-dibromo-25,26,27,28-四-正丙氧基杯[4]芳烃和5,11-双（二苯基膦基）-25,26,27， 28-四-正丙氧基杯[4]芳烃也已与M（COD）+（M = Rh，Ir）和RhCl（CO）片段配合。根据质谱和31 P NMR自旋晶格弛豫时间测量（T 1），发现所有复合物都是二聚体。分子建模提供的证据表明环应力比单体更有利于二聚体，并且通过比较Ir（COD）+物种在77 K时的光物理特性，证实了1,2-和1,3-异构体的建模结构。对于1，3-异构体，在1-己烯存在下P 2 Ir（C C）2 +发光体的发射寿命的降低更
• Regioselective upper-rim functionalizations of calix[4]arene by diphenylphosphino groups
  作者：Jonathan Gagnon、Martin Vézina、Marc Drouin、Pierre D Harvey

  DOI：10.1139/v01-161

  日期：2001.10.1

  The regioselective upper-rim functionalization of calix[4]arene have been performed to prepare all the multisubstituted diphenylphosphine derivatives. In addition, the X-ray structures of 5,17-dibromo-11,23-bis(diphenylphosphino)-25,26,27,28-tetra-n-propoxycalix[4]arene and 5,11,17,23-tetrakis(diphenylphosphino)-25,26,27,28-tetra-i-propoxy-calix[4]arene have been determined. Regioselective functionalizations have been achieved using methods that involve appropriate choices of bases, alkyllithium-solvent systems, stoichiometry, and reaction times. A new and convenient method for selectively preparing derivitized calix[4]arenes at proximal positions in relative large scale quantity has been developed and involves a transesterification of the distal diester derivative into the proximal isomer.Key words: calix[4]arenes, phosphine, upper-rim, X-ray structure, transesterification.

  对calix[4]arene的上缘选择性官能化已经进行，以制备所有多取代二苯基膦衍生物。此外，已确定了5,17-二溴-11,23-双(二苯基膦基)-25,26,27,28-四-n-丙氧基calix[4]arene和5,11,17,23-四(二苯基膦基)-25,26,27,28-四异丙氧基calix[4]arene的X射线结构。通过适当选择碱、烷基锂-溶剂系统、化学计量、反应时间等方法实现了选择性官能化。开发了一种新的便捷方法，可在相对较大规模上选择性地制备calix[4]arenes的衍生物，涉及将远端二酯衍生物转酯化为近端异构体。关键词：calix[4]arenes、膦、上缘、X射线结构、转酯化。
• Calixarene-monophosphines as supramolecular chelators
  作者：Soheila Sameni、Manuel Lejeune、Catherine Jeunesse、Dominique Matt、Richard Welter

  DOI：10.1039/b907100h

  日期：——

  The calix[4]arenes 5-diphenylphosphino-17-R1-11,23-diR2-25,26,27,28-tetrapropoxycalix[4]arene (1, R1 = R2 = Br; 2, R1 = Br, R2 = H; 3, R1 = R2 = p-tolyl; 4, R1 = p-tolyl, R2 = H; 5, R1 = R2 = H; 20, R1 = p-tolyl, R2 = H), all bearing a diphenylphosphino group attached to the calixarene upper rim, have been synthesised starting from 5,11,17,23-tetrabromo-25,26,27,28-tetrapropoxycalix[4]arene. Reaction of 1–5 with [RuCl2(p-cymene)]2 leads quantitatively to monophosphine complexes, [RuCl2(p-cymene)L], in which the endo-oriented ruthenium atom unit sits inside the cone delineated by the four phenoxy rings. The particular orientation of the P–Ru vector appears to result from π–π interactions between the p-cymene ligand and two aromatic cavity walls. Overall, in each case the calixarene end of the ligand behaves as a supramolecular receptor towards the Ru(p-cymene) fragment. Formation of complexes with exo-oriented P–M bonds were observed in the complexes cis-[PtCl2·12] and in [RuCl2(p-cymene)·20]. As shown by a variable temperature study carried out on [RuCl2(p-cymene)·3], in which the ruthenium is embedded in an expanded cone, the p-cymene ring undergoes a fast oscillation about the Ru-arene bond which can be frozen out at low temperatures. Reaction of [RuCl2(p-cymene)·3] with AgBF4 in CH3CN results in an intra-cavity reaction, with one chloride ligand being replaced by acetonitrile.

  合成了多种具有二苯基膦基团的钙木[4]芳烃，结构为5-二苯基膦基-17-R1-11,23-二R2-25,26,27,28-四丙氧基钙木[4]芳烃（1, R1 = R2 = Br；2, R1 = Br, R2 = H；3, R1 = R2 = 对甲基苯基；4, R1 = 对甲基苯基, R2 = H；5, R1 = R2 = H；20, R1 = 对甲基苯基, R2 = H），这些化合物是从5,11,17,23-四溴-25,26,27,28-四丙氧基钙木[4]芳烃出发合成的。1-5与[RuCl2(p-cymene)]2的反应定量生成了单膦配合物[RuCl2(p-cymene)L]，其中内向的钌原子单元位于由四个酚氧基环界定的锥体内部。P–Ru矢量的特定取向似乎是由p-茨烯配体与两个芳香腔壁之间的π–π相互作用所造成的。总体而言，在每种情况下，配体的钙木芳烃末端表现出对Ru(p-cymene)片段的超分子识别能力。在顺式-[PtCl2·12]和[RuCl2(p-cymene)·20]配合物中观察到了与外向P–M键形成的现象。通过对[RuCl2(p-cymene)·3]进行的变温研究显示，钌被嵌入一个扩展的锥体中，p-茨烯环围绕Ru-芳香环键发生快速振荡，这种振荡可以在低温下被冻结。[RuCl2(p-cymene)·3]与AgBF4在CH3CN中的反应导致腔内反应，其中一个氯配体被乙腈取代。