5,11,17,23-tetra-tert-butyl-25,27-diethoxycarbonylmethoxy-26,28-bis(diphenylphosphinito)calix[4]arene | 175477-22-2

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 5,11,17,23-tetra-tert-butyl-25,27-diethoxycarbonylmethoxy-26,28-bis(diphenylphosphinito)calix[4]arene
• 英文别名: 5,11,17,23-tetrakis-tert-butyl-25,27-bis(diphenylphosphinooxy)-26,28-bis(ethoxycarbonylmethoxy)calix[4]arene；Ethyl 2-[[5,11,17,23-tetratert-butyl-26,28-bis(diphenylphosphanyloxy)-27-(2-ethoxy-2-oxoethoxy)-25-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]oxy]acetate
• CAS: 175477-22-2
• 化学式: C₇₆H₈₆O₈P₂
• 分子量: 1189.46
• InChiKey: AYSQHIUJZBHXLZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  20.9
• 重原子数：
  86
• 可旋转键数：
  22
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.34
• 拓扑面积：
  89.5
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  二(氰基苯)二氯化钯 、 5,11,17,23-tetra-tert-butyl-25,27-diethoxycarbonylmethoxy-26,28-bis(diphenylphosphinito)calix[4]arene 以 四氢呋喃 为溶剂， 以90%的产率得到
  参考文献：
  名称：

  Transition–metal complexation by calix[4]arene-derived phosphinites

  摘要：

  A series of 26,28-di(alkoxy)-5,11,17,23-tetra-tert-butyl-25,27-bis(diphenylphosphinooxy)calix[4]arenes [alkoxy = OH L(10), OMe L(11), OEt L(12),OPr(n)L(13), OCH(2)CO(2)MeL(14), OCH(2)CO(2)EtL(15) or (-)-OCH(2)CO(2)C(10)H(19)L(16)(C10H19 = menthyl = 2-isopropyl-5-methylcyclohexyl)] and 28-(alkoxy)-5,11,17,23-tetra-tert-butyl-25,27-bis(diphenylphosphinooxy)-26-ethoxycalix[4]arenes [alkoxy = OCH(2)CO(2)Et L(17) or (-)-OCH2CO2C10H19 L(18)] have been prepared selectively as cone conformers b; treating the corresponding 25,27-dihydroxycalix[4] arene precursor with LiNPr2i or LiBu at temperatures below -50 degrees C, followed by reaction with PPh(2)Cl. All compounds exist in solution in a stable cone conformation, except L(11) for which a fast exchange between the cone conformer and a partial-cone isomer occurs. Phosphination of 5,11,17,23-tetra-tert-butyl-25,27-di(ethoxycarbonylmethoxy)-26,28-dihydroxycalix[4]arene L(6) using NEt(3) instead of LiNP2i, gave 5,11,17,23-tetra-tert-butyl-25-diphenylphos 27-hydroxycalix[4]arene L(19). When the reaction leading to L(10) was performed in refluxing tetrahydrofuran (thf), the 1,2-alternate conformer L(21) was formed in addition to L(10). As shown by a variable-temperature NMR study, L(21) undergoes fast homomerization in solution. Reaction of [MCl(2)(PhCN)(2)] (M = Pt or Pd) with 2 equivalents of monophosphinite L(19) gave selectively the corresponding trans-[MCl(2)L(2)(19)] complexes (M = Pt or Pd). For the diphosphinites, it was found that their complexation properties depend on both the calixarene substituents and the nature of the starting complex. Thus, reaction of the C-2 symmetrical diphosphinites L(12), L(15) and L(16) with [PtCl2(PhCN)(2)] gave cyclooligomeric complexes of formula [{trans-PtCl2(diphosphinite)}(4)] in which the diphosphinites behave as bridging ligands between two metal centres. Reaction of L(15) with [PdCl2(PhCN)(2)] gave [(trans-PdCl(2)L(17))(2)]. When the unsymmetrically substituted diphosphinite L(17) was treated with [PtCl2(PhCN)(2)], the dimer [(trans-PtCl(2)L(17))(2)] was formed. Diphosphinite L(18) and [PdCl2(PhCN)(2)] gave [(trans-PdCl(2)L(18))(2)]. Chelating behaviour was found for the chiral diphosphinite L(16) in [Rh(cod)L(16)]BF4 (cod = cycloocta-1,5-diene) obtained by reaction of [{RhCl(cod)}(2)]with 2 equivalents of AgBF4 and 2 equivalents of L(16) in thf.

  DOI：

  10.1039/dt9960000513
• 作为产物：
  描述：

  5,11,17,23-tetra-tert-butyl-25,27-di(ethoxycarbonylmethoxy)-26,28-dihydroxycalix[4]arene 、 二苯基氯化膦 在 正丁基锂 、 二异丙胺 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 生成 5,11,17,23-tetra-tert-butyl-25,27-diethoxycarbonylmethoxy-26,28-bis(diphenylphosphinito)calix[4]arene
  参考文献：
  名称：

  基于远端官能化杯[4]芳烃的双亚磷酸酯和双亚膦酸酯：配位化学及其在铑催化的低压烯烃加氢甲酰化中的应用

  摘要：

  六杯[4]芳烃，每个轴承的两个非环状PR 2个附接在远侧酚氧原子的单元，p -Bu吨-calix [4]芳烃- 25,27-（OPR 2）2 -26,28-（OR' ）2 （R = OPh； R'= Pr n，L 1 111； R = OPh； R'= CH 2 CO 2 Et，L 2 22； R = OPh； R'= CO 2胆固醇，L 3 33； R = Ph; R'= Pr n，L 4 44 ; R = Ph; R'= CH 2 CO 2Et，L 5 55 ; R = Ph; 合成了R'= CO 2胆固醇基，L 6 66）并研究了它们的配位性能。P中心被12个键隔开的L 1 111 – L 3 33二亚磷酸酯很容易形成螯合物，只要通过使用具有良好离去基团的起始络合物或在高稀释度下进行操作来实现络合反应即可避免形成低聚物。因此，阳离子络合物[Rh（COD）L 1 111 ] BF 4和[Rh（COD）L

  DOI：

  10.1039/b419284b

文献信息

• Multifunctional calixarene-derived phosphinites
  作者：Dominique Matt、Cyrille Loeber、Jacques Vicens、Zouhair Asfari

  DOI：10.1039/c39930000604

  日期：——

  The syntheses of unprecedented di and tri-functional phosphinites derived from p-tert-butylcalix[4]arene are described.

  本文描述了由对叔丁基杯[4]芳烃衍生出的前所未有的二官能和三官能膦的合成。
• Preparation, luminescence and interactions with Li+, Na+ and U022+ of two new metallocalix[4]arene complexes of iridium(I)
  作者：Jonathan Gagnon、Cyrille Loeber、Dominique Matt、Pierre D. Harvey

  DOI：10.1016/0020-1693(95)04858-8

  日期：1996.2

  Abstract Two new complexes of Ir(I) using diphosphine and diphosphinite calix[4]arene ligands have been prepared and characterized. The luminescent lowest energy excited MLCT state (metal-to-ligand charge transfer) has been addressed theoretically by extended Huckel molecular orbital calculations (EHMO), and a Franck-Condon analysis on the absorption spectra using the time dependent Heller's theory

  摘要制备并表征了使用二膦和二亚膦酸杯杯[4]芳烃配体制备的Ir（I）的两种新型配合物。理论上已经通过扩展的Huckel分子轨道计算（EHMO）解决了发光最低能量激发的MLCT状态（金属到配体的电荷转移），并使用时变的Heller理论对吸收光谱进行了Franck-Condon分析。 。通过添加底物（U0 2 2+，Li +，Na +），研究了两种络合物在77 K乙醇中对re的扰动。随添加底物而变化的幅度随U0 2 2+> Li +> Na +的变化而变化。