p-tert-butyl-calix[4]arene phosphite | 135839-87-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 酚类
• 英文名称: p-tert-butyl-calix[4]arene phosphite
• 英文别名: p-tert-butylcalix[4]arene phosphite；6,12,18,24-Tetratert-butyl-2,28,29-trioxa-1-phosphaheptacyclo[14.12.2.14,26.110,14.03,8.020,30.022,27]dotriaconta-3(8),4,6,10,12,14(32),16(30),17,19,22(27),23,25-dodecaen-32-ol
• CAS: 135839-87-1
• 化学式: C₄₄H₅₃O₄P
• 分子量: 676.876
• InChiKey: BPWWBQYBARDVKQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  13.8
• 重原子数：
  49
• 可旋转键数：
  4
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  47.9
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  p-tert-butyl-calix[4]arene phosphite 在 叔丁基过氧化氢 作用下， 生成
  参考文献：
  名称：

  Khasnis, Dilip V.; Burton, Jonathan M.; McNeil, Jeffrey D., Phosphorus, Sulfur and Silicon and the Related Elements, 1993, vol. 75, # 1-4, p. 253 - 256

  摘要：

  DOI：
• 作为产物：
  描述：

  反应 2.0h， 以99%的产率得到p-tert-butyl-calix[4]arene phosphite
  参考文献：
  名称：

  Direct transformation of six- to three-coordinate phosphorus in p-tert-butylcalix[4]arene; the first X-ray crystal structure of a hypervalent main group atom bound to a calixarene

  摘要：

  将二甲基胺从齐聚物六配位磷物种 p-fert-butylcalix[4]areneP(H)NHMe21 中移除，可得到三配位衍生物 p-tert- butylcalix[4]arene(H)P 4；Li[p-tert-butylcalix[4]areneP(H)NMe2]3 的 X 射线结构让我们了解到为什么没有观察到五配位物种。

  DOI：

  10.1039/c39910000562

文献信息

• NMR and X-ray crystallographic studies of unsymmetrical 25,26;27,28-dibridged para-tert-butyl calix[4]arene bisphosphites with a large “through-space” P–P coupling
  作者：Pathik Maji、Setharampattu S. Krishnamurthy、Munirathinam Nethaji

  DOI：10.1039/b903771c

  日期：——

  Three 25,26-bridged para-tert-butyl-calix[4]arene phosphites, 1–3, have been synthesized by linking two proximal phenolic oxygen atoms of para-tert-butyl-calix[4]arene to a P(OR) [R = 2,6-But2–4-Me-C6H2 (1), 2,6-Pri2-C6H3 (2) or 2,4-But2-C6H3 (3)] moiety. NMR spectroscopic data and X-ray crystallographic studies (1 and 2 only) show that the calixarene framework in 1 adopts a cone conformation, whereas in 2 and 3 it assumes a partial cone conformation. Unsymmetrical 25,26;27,28-dibridged para-tert-butyl-calix[4]arene bisphosphites 5–7 have been synthesized by the reaction of 25,26-bridged para-tert-butyl-calix[4]arene phosphite 1 with (R′O)PCl2 [R′ = 2,4-But2-C6H3 (5), 2,6-Pri2-C6H3 (6) or (1R,2S,5R)-(−)menthyl (7)]. NMR investigations (homonuclear 31P COSY) revealed an unprecedented “through-space” phosphorus–phosphorus coupling of 223–244 Hz for these unsymmetrical 25,26;27,28-dibridged para-tert-butyl-calix[4]arene bisphosphites. The molecular structure of unsymmetrical 25,26;27,28-bridged bisphosphite 5 was determined by X-ray crystallography; the two phosphorus atoms are in close proximity and the P⋯P distance (3.543(2) Å) is less than the sum of their van der Walls radii.

  通过将对叔丁基杯[4]芳烃的两个近端酚羟基氧原子连接到P(OR) [R = 2,6-二丁基-4-甲基苯(1), 2,6-二异丙基苯(2)或2,4-二丁基苯(3)]基团上，合成了三种25,26-桥联的对叔丁基杯[4]芳烃膦酸酯1-3。核磁共振(NMR)光谱数据和X射线晶体学研究(仅1和2)显示，1中的杯芳烃骨架采用圆锥构型，而在2和3中则为部分圆锥构型。通过25,26-桥联的对叔丁基杯[4]芳烃膦酸酯1与(R'O)PCl2 [R' = 2,4-二丁基苯(5), 2,6-二异丙基苯(6)或(1R,2S,5R)-(+)-薄荷基(7)]反应，合成了三种不对称25,26;27,28-双桥联的对叔丁基杯[4]芳烃双膦酸酯5-7。NMR研究(同核31P COSY)揭示了这些不对称25,26;27,28-双桥联的对叔丁基杯[4]芳烃双膦酸酯中前所未有的“跨空间”磷-磷耦合，耦合常数为223-244 Hz。通过X射线晶体学确定了不对称25,26;27,28-双桥联双膦酸酯5的分子结构;两个磷原子距离很近，P···P距离(3.543(2) Å)小于它们范德华半径之和。
• Calix[4]arene based monophosphites, identification of three conformations and their use in the rhodium-catalysed hydroformylation of 1-octene
  作者：Floris J. Parlevliet、Christoph Kiener、Jan Fraanje、Kees Goubitz、Martin Lutz、Anthony L. Spek、Paul C. J. Kamer、Piet W. N. M. van Leeuwen

  DOI：10.1039/a909103c

  日期：——

  insight into the 3-dimensional structure of two of these conformations. The three conformations were characterised by 1H, 13C and 31P NMR spectroscopy. NMR experiments showed that several of the phosphites are flexible showing fluxional behaviour of the molecular backbone in solution, but no interconversion between the different conformers was observed. The conformation of the product in the phosphite synthesis

  按照两条合成路线，合成了八种基于杯[4]芳烃骨架的单齿亚磷酸酯（2–9）。在所应用的反应条件下，六种构型中只有三种实际上形成。X射线分析两个构象体（4和5）中的一个提供了对这些构象中两个构象的3维结构的洞察力。这三个构象的特征是1 H，13 C和31 P NMR光谱。 核磁共振实验表明，几种亚磷酸酯具有柔性，显示了溶液中分子骨架的流动行为，但未观察到不同构象异构体之间的相互转化。亚磷酸酯合成中产物的构象是在磷原子与杯[4]芳烃（亚磷酰胺）的两个羟基连接的点确定的。这样的中间体磷酰胺（12）在4和5的合成中被分离出来。亚磷酸酯3-6，8和9中进行了测试铑催化加氢甲酰化。速率差异可以与配体。
• Rhodium(I) complexes of robust phosphites derived from calix[4]arenes and their application in the hydroformylation of 1-hexene
  作者：Christopher J. Cobley、Dianne D. Ellis、A. Guy Orpen、Paul G. Pringle

  DOI：10.1039/a908961f

  日期：——

  The monophosphites derived from calix[4]arene (Laa) and p-tert-butylcalix[4]arene (Lbbb) react with [Rh(CO)2(acac*)] (acac* = ButCOCHCOBut) to give the mononuclear complexes [Rh(CO)(Laa)(acac*)] and [Rh(CO)(Lbbb)(acac*)] respectively. The crystal structure of [Rh(CO)(Lbbb)(acac*)] shows the calixarene conformation to have aryl groups in down, out, up, up} orientations with one aryl blocking the axial site at the square planar metal. Treatment of [Rh2(μ-Cl)2(CO)4] with Lbbb gives an equilibrium mixture of products which have been assigned to the cis/trans isomers of [Rh2(μ-Cl)2(CO)2(Lbbb)2]. The crystal structure of cis-[Rh2(μ-Cl)2(CO)2(Lbbb)2] has a folded dimer geometry with both the concave and convex faces of the dimer partly blocked by the calixarene phosphite ligand. The rhodium complexes of Laa and Lbbb are very active and chemoselective catalysts for the hydroformylation of hexene but the regioselectivity is low.

  由萼[4]炔（Laa）和对叔丁基萼[4]炔（Lbbb）衍生的单磷酸盐与[Rh(CO)2(acac*)]（acac* = ButCOCHCOBut）反应，分别生成单核络合物[Rh(CO)(Laa)(acac*)]和[Rh(CO)(Lbbb)(acac*)]。从[Rh(CO)(Lbbb)(acac*)]的晶体结构可以看出，萼片烯构象中的芳基呈向下、向外、向上、向上}方向，其中一个芳基堵塞了方形平面金属的轴向位点。用 Lbbb 处理[Rh2(μ-Cl)2(CO)4]会产生一种平衡混合产物，这些产物被归类为[Rh2(μ-Cl)2(CO)2(Lbbb)2]的顺式/反式异构体。顺式[Rh2(μ-Cl)2(CO)2(Lbbb)2]的晶体结构具有折叠的二聚体几何形状，二聚体的凹面和凸面部分被钙烯丙基亚磷酸配体阻挡。Laa 和 Lbbb 的铑配合物是非常活跃的己烯加氢甲酰化化学选择性催化剂，但其区域选择性较低。
• Calix[4]arene derived phosphites: their hydrolytic stability and complexes with gold(I), platinum(II,0), palladium(II) and iridium(I)
  作者：Christopher J. Cobley、Dianne D. Ellis、A. Guy Orpen、Paul G. Pringle

  DOI：10.1039/a908960h

  日期：——

  K[PtCl3(C2H4)] with Laa gives the mononuclear cis-[PtCl2(Laa)2] whereas Lbb gives the binuclear trans-[Pt2Cl2(μ-Cl)2(Lbb)2]. The platinum(0) complexes [Pt(L)(nor)2] and [Pt(L)2(nor)] (L = Laa or Lbb, nor = norbornene) have been characterised in solution by 31P and 195Pt NMR spectroscopy. Treatment of [PdCl2(NCPh)2] with Laa gives a poorly soluble complex assigned the structure [PdCl2(Laa)2]. Treatment

  在单亚磷酸酯的改进的合成大号一个一和大号b b衍生自杯[4]芳烃 和 对叔丁基杯[4]芳烃分别报道。既大号一个一和大号b b是即使在回流的热稳定的和稳定的空气甲苯; 此外，它们不会被HCl水溶液或氢氧化钠。由[AuCl（tht）]可以很容易地制备两个配位的金（I）络合物[AuCl（L a a）]和[AuCl（L b b）]（tht = 四氢噻吩）。用L a a处理K [PtCl 3（C 2 H 4）]可得到单核顺- [PtCl 2（L a a）2 ]，而L b b可得到双核反式- [Pt 2 Cl 2（μ-Cl） ）2（L b b）2 ]。铂（0）络合物[Pt（L）（nor）2 ]和[Pt（L）2（nor）]（L  =  La a或L b b，也不= 降冰片烯）在溶液中的特征是31 P和195 Pt NMR光谱。的治疗[的PdCl 2（NCPH）2 ]与大号一个一个给出难溶复杂分配结构[的PdCl
• Variable Coordination of Phosphorus within Calixarenes and Complexing Abilities of Phosphorus-Based Calixarenes
  作者：Maomian Fan、Hongming Zhang、Michael Lattman

  DOI：10.1080/10426509908546230

  日期：1999.1.1

  Solvent-dependent coordination of phosphorus within a calix[4]arene cavity is shown and the differences in the abilities of a ligand to bind to a metal within calix[4]arenes and calix[5]arenes is demonstrated.