2-(diphenylphosphinyl)oxymethylpyridine | 280743-81-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: 2-(diphenylphosphinyl)oxymethylpyridine
• 英文别名: 2-methyloxy(diphenylphosphino)pyridine；Phosphine, diphenyl-[(2-pyridyl)methoxy]-；diphenyl(pyridin-2-ylmethoxy)phosphane
• CAS: 280743-81-9
• 化学式: C₁₈H₁₆NOP
• 分子量: 293.305
• InChiKey: HRPZEWYCGQSHEC-UHFFFAOYSA-N

物化性质

• 沸点：
  423.7±47.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  21
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.06
• 拓扑面积：
  22.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  乙二醇二甲醚溴化镍 、 2-(diphenylphosphinyl)oxymethylpyridine 以 二氯甲烷 为溶剂， 以72%的产率得到[Ni(2-methyloxy(diphenylphosphino)pyridine)Br2]
  参考文献：
  名称：

  Mono- and Dinuclear Nickel Complexes with Phosphino-, Phosphinito-, and Phosphonitopyridine Ligands: Synthesis, Structures, and Catalytic Oligomerization of Ethylene

  摘要：

  The P,N-type ligands 2-[(diphenylphosphino)methyllpyridine (12), 2-[2-(diphenylphosphino)ethyl]pyridine (13), 2-methyloxy(diphenylphosphino)pyridine (14), 2-methyloxy(dibenzyl-1,2-oxaphosphorino)pyridine (15), and 2-methyloxy(di-tert-butylphosphino)pyridine (16) have been prepared in good yields, and 12 and 13 have been used to synthesize Ni(II) complexes of formula [Ni(P,N)Cl-2], 17 (P,N = 12) and 18 (P,N = 13), by reaction with NiCl2 in methanol. The crystal structure of 18 has been determined by X-ray diffraction to be dinuclear with a distorted square-base pyramidal geometry around the Ni(II) centers. To examine the possible influence of the nature of the spacer link between the P and N donor atoms, we compared ligand 13, with a CH2CH2,, spacer, with 14 and 16, which have a isosteric CH2-O spacer. Reactions of the phosphinitopyridine ligands 14 and 16 and of the phosphonitopyridine 15 with [NiX2(DME)] (X = Cl or Br) afforded the complexes [Ni(P,N)Cl-2] 20 (X = Cl; P,N = 14), 21 (X = Br; P,N = 14), 22 (X = Cl; P,N = 16), and 23 (X = Cl; P,N = 15), respectively. The mononuclear structure of complex 22 has been established by X-ray diffraction and showed a distorted tetrahedral geometry around the metal center. Complexes 17, 18, and 20-22 have been tested as precatalysts in the oligornerization of ethylene, with AlEtCl2 or MAO as cocatalyst, in order to evaluate the influence of the stereoelectronic properties of the phosphorus substituents. With only 6 equiv of AlEtCl2, as cocatalyst and 4 x 10(-5) Mol precatalyst, complex 18 was the most active, with turnover frequencies (TOF) up to 91 200 C2H4/(mol Ni center dot h), and 20 with 2 equiv of AlEtCl2 showed the highest selectivities for ethylene dimers (up to 97%) and in 1-butene (up to 72%). When only 10(-5) mol precatalyst was used, the TOF values went up to 207 600 for 18 and 150 100 for 20. With only 25 equiv of MAO as cocatalyst, complex 18 was again the most active, with TOF values up to 20 600 C2H4/(mol Ni center dot h). Despite the high selectivity for C-4 olefins of 17, 18, 20, and 21 (up to 93% for 20), 22 presented the best selectivities for 1-butene (up to 73%) with MAO as cocatalyst, and its high reactivity for the reinsertion of 1-butene resulted in 2-ethyl-1-butene being the main product of the catalytic reaction (up to 91%).

  DOI：

  10.1021/om7008759
• 作为产物：
  描述：

  二苯基氯化膦 以 乙醚 、 二氯甲烷 为溶剂， 反应 1.0h， 生成 2-(diphenylphosphinyl)oxymethylpyridine
  参考文献：
  名称：

  2,6-二甲基-1,4-苯醌新型氧化还原缩合反应从大醇和羧酸制备各种羧酸酯

  摘要：

  使用 2,6-二甲基-1,4-苯醌 (DMBQ)、羧酸和原位形成的烷氧基二苯基膦 (1) 的新型氧化还原缩合反应顺利进行，得到相应的羧酸酯的产率很高。烷氧基二苯基膦是通过用伯醇或仲醇处理 N,N-二甲基氨基二苯基膦 (Ph2PNMe2) 或用伯醇、仲醇和叔醇的锂盐处理氯二苯基膦原位形成的。

  DOI：

  10.1246/cl.2003.300

文献信息

• Preparation of Various Carboxylic Acid Esters from Bulky Alcohols and Carboxylic Acids by a New Type Oxidation-reduction Condensation Using 2,6-Dimethyl-1,4-benzoquinone
  作者：Teruaki Mukaiyama、Wataru Kikuchi、Taichi Shintou

  DOI：10.1246/cl.2003.300

  日期：2003.3

  A new-type oxidation-reduction condensation by using 2,6-dimethyl-1,4-benzoquinone (DMBQ), carboxylic acids and in situ formed alkoxydiphenylphosphines (1) including the bulky alkoxy group-substituted ones proceeded smoothly to afford the corresponding carboxylic acid esters in good to high yields. Alkoxydiphenylphosphines were formed in situ by treating either N,N-dimethylaminodiphenylphosphine (Ph2PNMe2)

  使用 2,6-二甲基-1,4-苯醌 (DMBQ)、羧酸和原位形成的烷氧基二苯基膦 (1) 的新型氧化还原缩合反应顺利进行，得到相应的羧酸酯的产率很高。烷氧基二苯基膦是通过用伯醇或仲醇处理 N,N-二甲基氨基二苯基膦 (Ph2PNMe2) 或用伯醇、仲醇和叔醇的锂盐处理氯二苯基膦原位形成的。
• Bite angle effect of bidentate P–N ligands in palladium catalysed allylic alkylation †
  作者：Richard J. van Haaren、Cees J. M. Druijven、Gino P. F. van Strijdonck、Henk Oevering、Joost N. H. Reek、Paul C. J. Kamer、Piet W. N. M. van Leeuwen

  DOI：10.1039/b001355m

  日期：——

  Two series of new bidentate P–N ligands have been synthesized. Application of these ligands in the palladium catalysed allylic alkylation of crotyl chloride and cinnamyl chloride leads to the preferential formation of the branched product. A larger bite angle of the ligand leads to higher regioselectivity. Stoichiometric alkylation of the complex [Pd(C4H7)p-MeOC6H4CN(CH2)4OPPh2}][O3SCF3] proceeds with 88% regioselectivity to the branched product.

  合成了两系列新的双齿P–N配体。这些配体在钯催化的烯丙基氯与克罗基氯和肉桂基氯的烷基化反应中，优先形成支化产物。配体的较大咬合角度导致更高的区域选择性。复合物[Pd(C4H7)p-MeOC6H4CN(CH2)4OPPh2}][O3SCF3]的计量烷基化反应以88%的区域选择性进行，形成支化产物。
• Metallkomplexe als Emittermaterialien
  申请人：cynora GmbH

  公开号：EP2933850A1

  公开（公告）日：2015-10-21

  Die Erfindung betrifft ein Molekül aufweisend eine Struktur der Formel A sowie dessen Verwendung in optoelektronischen Bauelementen, insbesondere OLEDs. wobei M/M' = unabhängig ausgewählt aus der Gruppe bestehend aus Cu, Ag, Au; X = unabhängig ausgewählt aus der Gruppe bestehend aus Cl, Br, I, Pseudohalogenide; E'/E" = unabhängig ausgewählt aus der Gruppe bestehend aus P, As; Z/Z' = unabhängig ausgewählt aus der Gruppe bestehend aus N oder C; wobei zwischen Z/Z' und N entweder eine Einfachbindung oder eine Doppelbindung vorhanden ist; B'/B" = Brücke mit mindestens 2 bis zu 17 Gliedern.

  本发明涉及一种具有式 A 结构的分子及其在光电元件（尤其是有机发光二极管）中的应用。 其中 M/M' = 独立选自由 Cu、Ag、Au 组成的组； X = 独立选自由 Cl、Br、I、拟卤化物组成的组； E'/E" = 独立选自由 P、As 组成的组； Z/Z' = 独立选自由 N 或 C 组成的组；其中 Z/Z' 和 N 之间是单键或双键； B'/B" = 至少有 2 个、最多有 17 个成员的桥。
• New palladacyclic complexes with pyridylphosphine ligands: crystal structures of [Pd(Azb)(Ph2POCH2Py-P,N)][PF6] and [Pd(Phpy)(Ph2PNHPy-P,N)][PF6]
  作者：Gregorio Sánchez、Joaquı́n Garcı́a、David Meseguer、José L. Serrano、Luis Garcı́a、José Pérez、Gregorio López

  DOI：10.1016/j.ica.2004.06.040

  日期：2004.12

  The synthesis of palladacyclic derivatives with the hybrid pyridylphosphine ligands Py(CH2)OPPh2 (a) and PyNHPPh2 (b) in a neutral P,N-chelating coordination mode has been achieved. Treatment of selected chloride-bridged cyclometallated precursors [Pd((CN)-N-boolean AND)(mu-Cl)](2) [(CN)-N-boolean AND=2-pyridinin-phenyl Phpy, I-compounds; 7,8-benzoquinolyl Bzq, II-compounds; phenylazophenyl Azb, III-compounds or 2-(2-oxazolinyl)phenyl Phox, IV-compounds] with a or b in the presence of stoichiometric KPF6 gave the mononuclear derivatives Ia-IVa and Ib-IVb. The crystal structures of compounds [Pd(Azb)(Ph2POCH2Py-P,N)][PF6] (IIIa) and [Pd(Phpy)(Ph2PNHPy-P,N)][PF6] (Ib) have been determined. The new palladacyclopentachene precursor [PdC4COOMe4}(CH3CN)(2)] (V) has been prepared starting from the polymeric complex [PdC4COOMe4}](n). Its usefulness in the preparation of new derivatives has been tested by means of the straightforward reaction with ligands (a) or (b) to give mononuclear compounds [PdC-4(COOMe)(4)}(Ph2POCH2Py-P,N)] (Va) and [PdC-4(COOMe)(4)}(Ph2PNHPy-P,N)] (Vb). The reactions of hydroxo-bridged precursors [Pd-2((CN)-N-boolean AND)(mu-OH)](2) or [Pd-2C-4(COOMe)(4)}(2) (mu-OH)(2)][NBu4](2) with PyNHPPh2 afforded mononuclear complexes Ic-Vc (PyNPPh2 = c ligand) in which a less common anionic P,N-binding mode is forced as a result of ligand deprotonation. The new complexes were characterised by partial elemental analyses and spectroscopic methods (IR, FAB, H-1 and P-31H-1} NMR). (C) 2004 Elsevier B.V. All rights reserved.
• Efficient Method for the Preparation of Carboxylic Acid Alkyl Esters or Alkyl Phenyl Ethers by a New-Type of Oxidation–Reduction Condensation Using 2,6-Dimethyl-1,4-benzoquinone and Alkoxydiphenylphosphines
  作者：Taichi Shintou、Wataru Kikuchi、Teruaki Mukaiyama

  DOI：10.1246/bcsj.76.1645

  日期：2003.8

  A new-type of oxidation–reduction condensation proceeded smoothly to afford carboxylic acid alkyl esters or alkyl phenyl ethers in good to high yields by combined use of alkoxydiphenylphosphines (1...

  一种新型氧化还原缩合反应顺利进行，通过结合使用烷氧基二苯基膦（1...