n-二十烷基二苯基膦 | 105624-98-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: n-二十烷基二苯基膦
• 英文名称: 1-eicosyldiphenylphosphine
• 英文别名: n-eicosyldiphenylphosphine；Icosyl(diphenyl)phosphane
• CAS: 105624-98-4
• 化学式: C₃₂H₅₁P
• 分子量: 466.731
• InChiKey: IWTRMWQSSODBEX-UHFFFAOYSA-N

物化性质

• 沸点：
  547.0±19.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  13
• 重原子数：
  33
• 可旋转键数：
  21
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  n-二十烷基二苯基膦 在 双氧水 作用下， 以 甲醇 为溶剂， 反应 2.0h， 以110 mg的产率得到1-eicosyldiphenylphosphine oxide
  参考文献：
  名称：

  Organolanthanide-Catalyzed Synthesis of Phosphine-Terminated Polyethylenes

  摘要：

  Organolanthanide-mediated hydrophosphination and ethylene polymerization are coupled in a catalytic cycle to produce diphenylphosphine-terminated polyethylenes. The resulting polymers were characterized by 1H, 13C, and 31P NMR, GPC, and DSC and compared spectroscopically to the model compound, 1-eicosyldiphenylphosphine oxide. High activities (107 g polymer/(mol Ln.atm ethylene.h)) and narrow polydispersities were observed in the polymerization/chain transfer process. Polyethylene molecular weights were found to be inversely proportional to diphenylphosphine concentration, supporting a chain transfer mechanism. The present discovery represents the first case in which an electron-rich phosphine functions efficiently as a chain transfer agent in a single-site fn/d0-mediated olefin polymerization process.

  DOI：

  10.1021/ja045965n
• 作为产物：
  描述：

  溴代二十烷 、 potassium diphenylphosphine 以 四氢呋喃 为溶剂， 生成 n-二十烷基二苯基膦
  参考文献：
  名称：

  Organolanthanide-Catalyzed Synthesis of Phosphine-Terminated Polyethylenes

  摘要：

  Organolanthanide-mediated hydrophosphination and ethylene polymerization are coupled in a catalytic cycle to produce diphenylphosphine-terminated polyethylenes. The resulting polymers were characterized by 1H, 13C, and 31P NMR, GPC, and DSC and compared spectroscopically to the model compound, 1-eicosyldiphenylphosphine oxide. High activities (107 g polymer/(mol Ln.atm ethylene.h)) and narrow polydispersities were observed in the polymerization/chain transfer process. Polyethylene molecular weights were found to be inversely proportional to diphenylphosphine concentration, supporting a chain transfer mechanism. The present discovery represents the first case in which an electron-rich phosphine functions efficiently as a chain transfer agent in a single-site fn/d0-mediated olefin polymerization process.

  DOI：

  10.1021/ja045965n

文献信息

• Addition of phosphines to alpha-olefins
  申请人：STAUFFER CHEMICAL COMPANY

  公开号：EP0194716A1

  公开（公告）日：1986-09-17

  There is disclosed an improved process for the addition of phospinesto alpha-olefins at high yields and conversions. The process involves the absence of a catalyst whose residues could interfere with the utility of the product, such as n-hexyldiphenylphosphine, as a ligand. Simple thermal reaction is used at temperatures of at least 200°C., most preferably 250°C - 350°C. The pressure is preferably at least atmospheric. Preferred reactants, pnoducts, and pracessing conditions are also disclosed. Batch processes are exemplified and continuous processes proposed.

  本发明公开了一种改进的α-烯烃加磷工艺，产量高，转化率高。该工艺不使用残留物会干扰产品效用的催化剂，如作为配体的正己基二苯基膦。简单的热反应温度至少为 200°C，最好为 250°C - 350°C。压力最好至少为大气压。此外，还公开了优选的反应物、配料和加工条件。举例说明了间歇式工艺，并提出了连续式工艺。
• Preparation of alkyldiarylphosphines and related compounds
  申请人：STAUFFER CHEMICAL COMPANY

  公开号：EP0196742A1

  公开（公告）日：1986-10-08

  A process is disclosed for preparing alkyldiarylphosphines and related compounds. In such process a compound having the structural formula: wherein : Z is an atom from group VA of the periodic table; Y is any radical that is essentially incapable of reacting with an alkali metal; X is any radical that is essentially incapable of reacting with an alkali metal; W is a substituted or unsubstituted aryl, alkyl, arylalkyl, or alkylaryl radical or hydrogen; and is prepared by reacting a first halide with a molten alkali metal or amalgam thereof in the presence of an inert solvent to form a first reacted mixture which is reacted with a second halide wherein an amount of the alkali metal or amalgam thereof is used in an excess of less than 100% and the yield of the product is greater than 70%. Typically, diphenylphosphinous chloride is reacted in solution with an excess of an alkali metal; and the reaction product reacted with chorohex- ane thereby forming hexyldiphenylphosphine. The improved process produces greater yields, by use of critical amounts of alkali metal; use of a single reactor rather than two reactors; preinitiation of the first stage reaction reduction of temperatures to increase reaction rate under certain conditions; and preferred reactants and physical form thereof. Novel products include behenyldiphenylphosphine.

  本发明公开了一种制备烷基叔基膦及相关化合物的工艺。在该工艺中，化合物的结构式为 其中： Z 是元素周期表 VA 族中的原子； Y 是基本上不能与碱金属反应的任何基团； X 是基本上不能与碱金属反应的任何基团； W 是取代或未取代的芳基、烷基、芳烷基或烷芳基或氢；以及 制备方法是：在惰性溶剂存在下，使第一种卤化物与熔融碱金属或其汞齐反应，形成第一种反应混合物，该混合物与第二种卤化物反应，其中碱金属或其汞齐的使用过量小于 100%，产物的收率大于 70%。通常，二苯基氯化膦在溶液中与过量的碱金属反应，反应产物与氯己烯反应，从而形成羟基二苯基膦。改进后的工艺产量更高，因为它使用了临界量的碱金属；使用了单个反应器而不是两个反应器；预引发了第一阶段反应，降低了温度以提高特定条件下的反应速率；以及优选的反应物及其物理形式。新产品包括苯基二苯基膦。
• Organolanthanide-Catalyzed Synthesis of Phosphine-Terminated Polyethylenes. Scope and Mechanism
  作者：Amber M. Kawaoka、Tobin J. Marks

  DOI：10.1021/ja044174i

  日期：2005.5.1

  Primary and secondary phosphines are investigated as chain-transfer agents for organolanthanide-mediated olefin polymerization. Ethylene polymerizations were carried out with [Cp'(2)LnH](2) and Cp'(2)LnCH(SiMe3)(2) (Cp' = eta(5)-Me5C5; Ln = La, Sm, Y, Lu) precatalysts in the presence of dicyclohexyl-, diisobutyl-, diethyl-, diphenyl-, cyclohexyl-, and phenylphosphine. In the presence of secondary phosphines, high polymerization activities (up to 10(7) g of polymer/(mol of Ln(.)atm ethylene(.)h)) and narrow product polymer polydispersities are observed. For lanthanocene-mediated ethylene polymerizations, the phosphine chain-transfer efficiency correlates with the rate of Ln-CH(SiMe3)(2) protonolysis by the same phosphines and follows the trend H2PPh >> H2PCy > HPPh2 > HPEt2 approximate to (HPBu2)-Bu-i > HPCy2. Under the conditions investigated, dicyclohexylphosphine is not an efficient chain-transfer agent for Cp'2LaPCy2- and Cp'2YPCy2-mediated ethylene polymerizations. Diisobutylphosphine and diethylphosphine are efficient chain-transfer agents for Cp'La-2-mediated polymerizations; however, phosphine chain transfer does not appear to be competitive with other chain-transfer pathways in Cp'Y-2-mediated polymerizations involving diisobutylphosphine. Regardless of the lanthanide metal, diphenylphosphine is an efficient chain-transfer agent for ethylene polymerization. Polymerizations conducted in the presence of primary phosphines produce only low-molecular-weight products. Thus, Cp'Y-2-mediated ethylene polymerizations conducted in the presence of phenylphosphine and cyclohexylphosphine produce low-molecular-weight phenylphosphine- and cyclohexylphosphine-capped oligomers, respectively. For Cp'2YPPh2-mediated ethylene polymerizations, a linear relationship is observed between M-n and [diphenylphosphine](-1), consistent with a phosphine protonolytic chain-transfer mechanism.
• ——
  作者：BAY W. E.、 REINEKE K. E.

  DOI：——

  日期：——
• US4618720A
  申请人：——

  公开号：US4618720A

  公开（公告）日：1986-10-21