(benzoylmethylene)phenyldimethylphosphorane | 59986-26-4

• 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: (benzoylmethylene)phenyldimethylphosphorane
• 英文别名: Dimethyl-phenacyliden-phenyl-phosphoran；-dimethyl-phenyl-phosphoran；Benzoylmethylenedimethylphenylphosphorane；2-[dimethyl(phenyl)-λ5-phosphanylidene]-1-phenylethanone
• CAS: 59986-26-4
• 化学式: C₁₆H₁₇OP
• 分子量: 256.284
• InChiKey: GWRHDAKLURMGFM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  降冰片烯 、 bis(1,5-cyclooctadiene)nickel (0) 、 (benzoylmethylene)phenyldimethylphosphorane 以 not given 为溶剂， 生成 [((CH3)2PCHC(C6H5)O)nickel(II)(phenyl)(norbornene)]
  参考文献：
  名称：

  Nickel catalysts for the addition polymerization of norbornene and its derivatives and for their copolymerization with ethylene

  摘要：

  The addition polymerization of norbornene and its derivatives has been carried out in the presence of a nickel complex or carboxylate and an electron acceptor to obtain amorphous polymers with bicyclic units. Norbornene copolymers with conjugated dienes or ethylene cannot be obtained with these catalysts because of rapid chain transfer reactions. Norbornene can be copolymerized with ethylene under mild conditions in the presence of nickel phosphorylide chelates without using any cocatalyst. In most cases, the backbone of the resulting copolymer consists of alternating comonomer units. The new catalysts allow ethylene to be copolymerized with norbornene derivatives containing ester substituents.

  DOI：

  10.1134/s0023158406020133
• 作为产物：
  描述：

  Phenacyl-dimethyl-phenyl-phosphonium 在 sodium hydride 作用下， 以 甲苯 为溶剂， 以3.800 g的产率得到(benzoylmethylene)phenyldimethylphosphorane
  参考文献：
  名称：

  SHOP-type nickel complexes with alkyl substituents on phosphorus, synthesis and catalyticethylene oligomerization

  摘要：

  (n-Bu)3PCHC(O)Ph 6，(t-Bu)2PhPCHC(O)Ph 7，(t-Bu)Ph2PCHC(O)Ph 8，(n-Bu)2PhPCHC(O)Ph 9、(n-Bu)Ph2PCHC(O)Ph 10、Me2PhPCHC(O)Ph 11 和 Ph3PCHC(O)(o-OMe-C6H4) 12 的合成，产率为 80-96%。[NiPh{Ph(n-Bu)2PCHC(O)Ph}(PPh3)] 16 和 [NiPh{Ph(n-Bu)PCHC(O)Ph}(PPh3)] 17 分别是通过等摩尔量的 [Ni(COD)2] 和 PPh3 与 β-酮磷酰化物 12 或 8-10 反应制备的，并通过 1H 和 31P{1H} NMR 光谱进行了表征。核磁共振光谱进行表征。核磁共振研究和 13 的晶体结构测定表明，C-H 基团 α 至磷的氢原子与醚官能团之间存在相互作用。[NiPh{Ph(n-Bu)PCHC(O)Ph}(Py)] 21 和 [NiPh{Me2PCHC(O)Ph}(Py)] 22 分别从 [Ni(COD)2] 和过量吡啶与 β-酮磷酰化物 Ph3PCHC(O)Ph 3 或 8-11 的反应中分离出来，并通过 1H 和 31P{1H} NMR 光谱进行了表征。核磁共振光谱进行表征。配体 3、8、10 和 12 在 30 或 60 巴的乙烯压力下与 1 个等量的 [Ni(COD)2] 和 PPh3 反应，用于原位制备低聚催化剂。由 12、[Ni(COD)2] 和 PPh3 原位制备的催化剂是该系列中活性最高的催化剂，在 30 巴乙烯条件下，其吨位为 12 700 摩尔 C2H4（摩尔 Ni）-1。在 30 巴乙烯条件下，β-酮磷 Ylide 8 与 3 个等量的 [Ni(COD)2] 和 1 个等量的 PPh3 原位反应，观察到乙烯聚合，吨当量为 5500 摩尔 C2H4（摩尔 Ni）-1。

  DOI：

  10.1039/b713451g

文献信息

• 246. The phosphobetaines: preparation and properties
  作者：S. Trippett、D. M. Walker

  DOI：10.1039/jr9610001266

  日期：——
• SHOP-type nickel complexes with alkyl substituents on phosphorus, synthesis and catalyticethylene oligomerization
  作者：Anthony Kermagoret、Pierre Braunstein

  DOI：10.1039/b713451g

  日期：——

  The β-keto phosphorus ylides (n-Bu)3PCHC(O)Ph 6, (t-Bu)2PhPCHC(O)Ph 7, (t-Bu)Ph2PCHC(O)Ph 8, (n-Bu)2PhPCHC(O)Ph 9, (n-Bu)Ph2PCHC(O)Ph 10, Me2PhPCHC(O)Ph 11 and Ph3PCHC(O)(o-OMe-C6H4) 12 have been synthesized in 80–96% yields. The Ni(II) complexes [NiPhPh2PCHC(O)(o-OMeC6H4)}(PPh3)] 13, [NiPhPh(t-Bu)PCHC(O)Ph}(PPh3)] 15, [NiPh(n-Bu)2PCHC(O)Ph}(PPh3)] 16 and [NiPhPh(n-Bu)PCHC(O)Ph}(PPh3)] 17 have been prepared by reaction of equimolar amounts of [Ni(COD)2] and PPh3 with the β-keto phosphorus ylides 12 or 8–10, respectively, and characterized by 1H and 31P1H} NMR spectroscopy. NMR studies and the crystal structure determination of 13 indicated an interaction between the hydrogen atom of the C–H group α to phosphorus and the ether function. The complexes [NiPhPh2PCHC(O)Ph}(Py)] 18, [NiPhPh(t-Bu)PCHC(O)Ph}(Py)] 19, [NiPh(n-Bu)2PCHC(O)Ph}(Py)] 20, [NiPhPh(n-Bu)PCHC(O)Ph}(Py)] 21 and [NiPhMe2PCHC(O)Ph}(Py)] 22 have been isolated from the reactions of [Ni(COD)2] and an excess of pyridine with the β-keto phosphorus ylides Ph3PCHC(O)Ph 3 or 8–11, respectively, and characterized by 1H and 31P1H} NMR spectroscopy. Ligands 3, 8, 10 and 12 have been used to prepare in situ oligomerization catalysts by reaction with one equiv. of [Ni(COD)2] and PPh3 under an ethylene pressure of 30 or 60 bar. The catalyst prepared in situ from 12, [Ni(COD)2] and PPh3 was the most active of the series with a TON of 12 700 mol C2H4 (mol Ni)−1 under 30 bar ethylene. When the β-keto phosphorus ylide 8 was reacted in situ with three equiv. of [Ni(COD)2] and one equiv. of PPh3 under 30 bar of ethylene, ethylene polymerization was observed with a TON of 5500 mol C2H4 (mol Ni)−1.

  (n-Bu)3PCHC(O)Ph 6，(t-Bu)2PhPCHC(O)Ph 7，(t-Bu)Ph2PCHC(O)Ph 8，(n-Bu)2PhPCHC(O)Ph 9、(n-Bu)Ph2PCHC(O)Ph 10、Me2PhPCHC(O)Ph 11 和 Ph3PCHC(O)(o-OMe-C6H4) 12 的合成，产率为 80-96%。[NiPhPh(n-Bu)2PCHC(O)Ph}(PPh3)] 16 和 [NiPhPh(n-Bu)PCHC(O)Ph}(PPh3)] 17 分别是通过等摩尔量的 [Ni(COD)2] 和 PPh3 与 β-酮磷酰化物 12 或 8-10 反应制备的，并通过 1H 和 31P1H} NMR 光谱进行了表征。核磁共振光谱进行表征。核磁共振研究和 13 的晶体结构测定表明，C-H 基团 α 至磷的氢原子与醚官能团之间存在相互作用。[NiPhPh(n-Bu)PCHC(O)Ph}(Py)] 21 和 [NiPhMe2PCHC(O)Ph}(Py)] 22 分别从 [Ni(COD)2] 和过量吡啶与 β-酮磷酰化物 Ph3PCHC(O)Ph 3 或 8-11 的反应中分离出来，并通过 1H 和 31P1H} NMR 光谱进行了表征。核磁共振光谱进行表征。配体 3、8、10 和 12 在 30 或 60 巴的乙烯压力下与 1 个等量的 [Ni(COD)2] 和 PPh3 反应，用于原位制备低聚催化剂。由 12、[Ni(COD)2] 和 PPh3 原位制备的催化剂是该系列中活性最高的催化剂，在 30 巴乙烯条件下，其吨位为 12 700 摩尔 C2H4（摩尔 Ni）-1。在 30 巴乙烯条件下，β-酮磷 Ylide 8 与 3 个等量的 [Ni(COD)2] 和 1 个等量的 PPh3 原位反应，观察到乙烯聚合，吨当量为 5500 摩尔 C2H4（摩尔 Ni）-1。
• Nickel catalysts for the addition polymerization of norbornene and its derivatives and for their copolymerization with ethylene
  作者：K. L. Makovetskii、V. I. Bykov、E. Sh. Finkel’shtein

  DOI：10.1134/s0023158406020133

  日期：2006.3

  The addition polymerization of norbornene and its derivatives has been carried out in the presence of a nickel complex or carboxylate and an electron acceptor to obtain amorphous polymers with bicyclic units. Norbornene copolymers with conjugated dienes or ethylene cannot be obtained with these catalysts because of rapid chain transfer reactions. Norbornene can be copolymerized with ethylene under mild conditions in the presence of nickel phosphorylide chelates without using any cocatalyst. In most cases, the backbone of the resulting copolymer consists of alternating comonomer units. The new catalysts allow ethylene to be copolymerized with norbornene derivatives containing ester substituents.