3-methyl-1-phenyl-4-triphenylphosphoranylidene-2-pyrazolin-5-one | 22401-05-4

• 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: 3-methyl-1-phenyl-4-triphenylphosphoranylidene-2-pyrazolin-5-one
• 英文别名: 3-methyl-1-phenyl-4-triphenylphosphorylidene-5-pyrazolone；5-methyl-2-phenyl-4-(triphenyl-λ⁵-phosphanylidene)-2,4-dihydro-pyrazol-3-one；5-Oxo-3-methyl-1-phenyl-4-triphenylphosphoranyliden-Δ²-pyrazolin；3-Methyl-1-phenyl-4-(triphenylphosphoranylidene)-1H-pyrazol-5(4H)-one；5-methyl-2-phenyl-4-(triphenyl-λ5-phosphanylidene)pyrazol-3-one
• CAS: 22401-05-4
• 化学式: C₂₈H₂₃N₂OP
• 分子量: 434.477
• InChiKey: DQWAUXVGPSVZCJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  32
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.04
• 拓扑面积：
  32.7
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  二(氰基苯)二氯化钯 、 3-methyl-1-phenyl-4-triphenylphosphoranylidene-2-pyrazolin-5-one 以 氯仿 为溶剂， 以55%的产率得到trans-dichloro-bis(3-methyl-1-phenyl-4-triphenylphosphoranylidene-2-pyrazolin-5-one)palladium(II)
  参考文献：
  名称：

  Can weak interactions modify the binding properties of a strong nitrogen donor? Unusual N-coordination of a phosphoranylidene-substituted pyrazolone unit towards palladium(ii) centres: an experimental and theoretical study

  摘要：

  在两种钯（II）配合物[PdCl2L2]（2）和[Pd(o-C6H4CH2NMe2)ClL]（3）中发现了 3-甲基-1-苯基-4-（三苯基膦亚基）-2-吡唑啉-5-酮（L）的选择性 N（2）结合。X 射线衍射研究表明，吡唑环几乎垂直于配位平面。在这两种配合物中，金属原子都位于吡唑环确定的平面之外（平面与 Pd-N 向量之间的二面角为 30°）。为了研究这种变形的原因，我们对复合物 2 的简化模型进行了理论研究，其中用 NH3 取代了单个吡唑酮配体。从这项研究中可以推断出，平面外畸变主要涉及一个氯原子和 N(1)-linked 苯基的一个正芳香族 H 原子之间以及另一个氯原子和 PPh3 基团的一个正芳香族 H 原子之间微弱的静电作用。

  DOI：

  10.1039/b506352n
• 作为产物：
  描述：

  alkaline earth salt of/the/ methylsulfuric acid 在 air 作用下， 以 甲苯 为溶剂， 反应 48.0h， 以70%的产率得到3-methyl-1-phenyl-4-triphenylphosphoranylidene-2-pyrazolin-5-one
  参考文献：
  名称：

  An Efficient Keim‐Type Catalyst Based on an Electron‐Poor P , O ‐Chelate; Tuning the Selectivity of Ethylene Oligomerisation towards Short α‐Olefins

  摘要：

  AbstractThe tertiary phosphane Ph2P‐pzONa, in which the phosphorus atom is substituted by an electron‐withdrawing pyrazol‐onato unit, reacts with trans‐[NiPhCl(PPh3)2] to afford quan‐titatively trans‐P,P'‐[NiPh(Ph2P‐pzO)(PPh3)] (4), the first Keim‐type catalyst derived from an amide. In the absence of any cocatalyst, complex 4 converts ethylene in high selectivity and activity into α‐olefins. The product distribution is drastically shifted towards lower oligomers when compared to the outcome of the reaction carried out with the conventional SHOP catalyst. Thus, when operating at 1 bar, over 99 wt.‐% of the oligomers formed are C4–C16 oligomers. In ethylene‐free solvents, 4 was shown to slowly undergo reductive elimination to produce the stabilised phosphorus ylide Ph3P‐pzO (5). Both compounds (4 and 5) were characterised by single‐crystal X‐ray diffraction analyses. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

  DOI：

  10.1002/ejic.200401015

文献信息

• A regioselective synthesis of 5-pyrazolones and pyrazoles from phosphazenes derived from hydrazines and acetylenic esters
  作者：Francisco Palacios、Ana M.Ochoa de Retana、Jaione Pagalday

  DOI：10.1016/s0040-4020(99)00890-x

  日期：1999.12

  Efficient and regioselective syntheses of 1-phenyl-5-pyrazolones substituted with a phosphoranylidene group in the 3-position and of 3-alkoxycarbonyl-5-methoxy-1-phenyl pyrazoles are described. The key step is the formation of functionalized hydrazones by [2+2] cycloaddition reaction of phosphazenes derived from hydrazines with acetylenic esters. Subsequent cyclization of these compounds with butyl

  描述了在3-位被磷亚烷基取代的1-苯基-5-吡唑啉酮和3-烷氧基羰基-5-甲氧基-1-苯基吡唑的高效和区域选择性合成。关键步骤是通过衍生自肼的磷腈与炔属酯的[2 + 2]环加成反应形成官能化的。随后用丁基锂将这些化合物环化，得到取代的5-吡唑啉酮，同时将它们与乙腈一起加热可形成区域选择性的3-烷氧基羰基-5-甲氧基-1-苯基吡唑。
• An Efficient Keim‐Type Catalyst Based on an Electron‐Poor <i>P</i> , <i>O</i> ‐Chelate; Tuning the Selectivity of Ethylene Oligomerisation towards Short α‐Olefins
  作者：Pierre Kuhn、David Sémeril、Catherine Jeunesse、Dominique Matt、Pierre Lutz、Richard Welter

  DOI：10.1002/ejic.200401015

  日期：2005.4

  AbstractThe tertiary phosphane Ph2P‐pzONa, in which the phosphorus atom is substituted by an electron‐withdrawing pyrazol‐onato unit, reacts with trans‐[NiPhCl(PPh3)2] to afford quan‐titatively trans‐P,P'‐[NiPh(Ph2P‐pzO)(PPh3)] (4), the first Keim‐type catalyst derived from an amide. In the absence of any cocatalyst, complex 4 converts ethylene in high selectivity and activity into α‐olefins. The product distribution is drastically shifted towards lower oligomers when compared to the outcome of the reaction carried out with the conventional SHOP catalyst. Thus, when operating at 1 bar, over 99 wt.‐% of the oligomers formed are C4–C16 oligomers. In ethylene‐free solvents, 4 was shown to slowly undergo reductive elimination to produce the stabilised phosphorus ylide Ph3P‐pzO (5). Both compounds (4 and 5) were characterised by single‐crystal X‐ray diffraction analyses. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
• Can weak interactions modify the binding properties of a strong nitrogen donor? Unusual N-coordination of a phosphoranylidene-substituted pyrazolone unit towards palladium(ii) centres: an experimental and theoretical study
  作者：Antonio J. Mota、Alain Dedieu、Pierre Kuhn、Dominique Matt、Richard Welter、Markus Neuburger

  DOI：10.1039/b506352n

  日期：——

  Selective N(2)-binding of 3-methyl-1-phenyl-4-(triphenylphosphoranylidene)-2-pyrazolin-5-one (L) has been found in two palladium(II) complexes, [PdCl2L2] (2) and [Pd(o-C6H4CH2NMe2)ClL] (3). X-Ray diffraction studies show that the pyrazole rings lie almost perpendicular to the coordination plane. In both complexes the metal atom is located out of the plane defined by the pyrazole ring(s) (dihedral angle between the plane and the Pd–N vector ∼30°). To investigate the origin of this distortion, a theoretical study was carried out on a simplified model of complex 2, where a single pyrazolone ligand was replaced by NH3. From this study it could be inferred that the out-of-plane distortion mainly involves weak, electrostatic interactions between a chlorine atom and an ortho-aromatic H atom of the N(1)-linked phenyl group, as well as between the other chlorine atom and an ortho-aromatic H atom of the PPh3 group.

  在两种钯（II）配合物[PdCl2L2]（2）和[Pd(o-C6H4CH2NMe2)ClL]（3）中发现了 3-甲基-1-苯基-4-（三苯基膦亚基）-2-吡唑啉-5-酮（L）的选择性 N（2）结合。X 射线衍射研究表明，吡唑环几乎垂直于配位平面。在这两种配合物中，金属原子都位于吡唑环确定的平面之外（平面与 Pd-N 向量之间的二面角为 30°）。为了研究这种变形的原因，我们对复合物 2 的简化模型进行了理论研究，其中用 NH3 取代了单个吡唑酮配体。从这项研究中可以推断出，平面外畸变主要涉及一个氯原子和 N(1)-linked 苯基的一个正芳香族 H 原子之间以及另一个氯原子和 PPh3 基团的一个正芳香族 H 原子之间微弱的静电作用。