1,2-bis(diphenylphosphinoethynyl)benzene

• 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: 1,2-bis(diphenylphosphinoethynyl)benzene
• 英文别名: bis((diphenylphosphino)ethynyl)benzene；dppeb；o-Bis(diphenyl-phosphino-ethynyl)benzene；2-[2-(2-diphenylphosphanylethynyl)phenyl]ethynyl-diphenylphosphane
• 化学式: C₃₄H₂₄P₂
• 分子量: 494.512
• InChiKey: PPRKOKBHNVOQHF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.5
• 重原子数：
  36
• 可旋转键数：
  8
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.0
• 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：

  1,2-bis(diphenylphosphinoethynyl)benzene 在 hydrazine 、 cyclohexadiene 作用下， 以 邻二氯苯 、 苯 为溶剂， 生成 trans-Pd((2-chlorophenyl)diphenylphosphine)2Cl2
  参考文献：
  名称：

  Structure and Thermal Reactivity of a Novel Pd(0) Metalloenediyne

  摘要：

  We report the X-ray diffraction structure and thermal reactivity of the metalloenediyne compound bis(1,2-bis(diphenylphosphinoethynyl)benzenepalladium(0) (Pd(dppeb)(2), 1). The structure of 1 features a tetrahedral Pd(0) center with four phosphorus atoms from two chelaling ligands. The P-Pd-P bond angles nearly match the idealized 109.5 degrees geometry expected for a d(10) metal center in a tetrahedral ligand field. The tetrahedral geometry of the metal center forces the alkyne termini separation of the enediyne ligand to a distance of 3.47 Angstrom, which results in a thermally stable compound at room temperature, However, at 115 degrees C 1 exhibits solvent-dependent reactivity. In sigma-fluorotoluene, 1 decomposes via ligand dissociation, while in sigma-dichlorobenzene, carbon-halide bond activation of solvent occurs leading to the oxidative addition product trans-Pd((2-chlorophenyl)diphenylphosphine)(2)Cl-2 and free (2-chlorophenyl)diphenylphosphine. The thermal reactivity of 1 is markedly more endothermic (44 kcal/mol) than that of the known Pd(dppeb)Cl-2 analogue (12.3 kcal/mol), The diminished reactivity can be attributed to two factors: the increased alkyne termini separation in 1 (3.47 vs 3.3 Angstrom) due to the metal-mandated tetrahedral geometry of the Pd(0) center, and the resistance of the Pd(0) to adopting a planar transition state geometry to promote Bergman cyclization. Overall this study demonstrates that metal binding can impose structural consequences upon the enediyne ligand governed by the oxidation state and corresponding ligand field geometry of the metal center.

  DOI：

  10.1021/ja9944094
• 作为产物：
  描述：

  1,2-bis(trimethylsilylethynyl)benzene 在 正丁基锂 、 potassium carbonate 作用下， 以 甲醇 、 乙醚 、 水 为溶剂， 反应 20.0h， 生成 1,2-bis(diphenylphosphinoethynyl)benzene
  参考文献：
  名称：

  Luminescent Coordination Glass: Remarkable Morphological Strategy for Assembled Eu(III) Complexes

  摘要：

  Syntheses of novel luminescent Eu(III) coordination glasses 1 ([Eu(hfa)(3)(o-dpeb)](2)), 2 ([Eu(hfa)(3)(m-dpeb)](3)), and 3 ([Eu(hfa)(3)(p-dpeb)](n)) are reported. They are composed of Eu(III) ions, hexafluoroacetylacetonato (hfa) ligands, and unique bent-angled phosphine oxide (o-, m-, p-dpeb) ligands with ethynyl groups. Their coordination structures and glass formability are dependent on the regiochemistry of substitution in regard to the internal benzene core. Single-crystal X-ray analyses and DFT calculation reveals dinuclear, trinuclear, and polymer structures for Eu(III) coordination glasses 1, 2, and 3, respectively. Those compounds show characteristic glass-transition (T-g = 25-96 degrees C) and strong luminescence properties (phi(Ln) = 72-94%).

  DOI：

  10.1021/acs.inorgchem.5b00145

文献信息

• Utilizing Redox-Mediated Bergman Cyclization toward the Development of Dual-Action Metalloenediyne Therapeutics
  作者：Sarah E. Lindahl、Hyunsoo Park、Maren Pink、Jeffrey M. Zaleski

  DOI：10.1021/ja308190q

  日期：2013.3.13

  cis-Bergman-cyclized, diiodo product 3 ((31)P: δ = 41 ppm, J(Pt-P) = 3346 Hz) with concomitant loss of 1 equiv of uncyclized phosphine chelate ((31)P: δ = -33 ppm). In contrast, addition of 2 equiv of I2 in the absence of additional radical trap instantaneously forms a metastable Pt(dppeb)2(2+) intermediate species, 4, that is characterized by δ = 51 ppm in the (31)P NMR (J(Pt-P) = 3171 Hz) and ν(C≡C) = 2169

  2 当量的 1,2-双（（二苯基膦基）乙炔基）苯 (dppeb, 1) 与 Pt(cod)Cl2 反应，然后用 N2H4 处理产生还原的 Pt(0) 金属二炔，Pt(dppeb)2, 2。由于接近理想化的四面体几何形状，该配合物在环境条件下对空气氧化和金属介导的伯格曼环化都是稳定的。在过量 1,4-环己二烯 (1,4-CHD) 自由基陷阱存在下，2 与 1 当量的 I2 反应快速且近乎定量地生成顺式伯格曼环化的二碘产物 3 ((31)P: δ = 41 ppm，J(Pt-P) = 3346 Hz)，同时损失 1 当量的未环化膦螯合物（(31)P：δ = -33 ppm）。相比之下，在没有额外自由基陷阱的情况下添加 2 当量的 I2 会立即形成亚稳态 Pt(dppeb)2(2+) 中间物种，4，在(31)P NMR (J(Pt-P) = 3171 Hz) 和 ν(C≡C) = 2169 cm(-1)
• Compounds, composition, and methods for photodynamic therapy
  申请人：Advanced Research and Technology Institute, Inc.

  公开号：US06828439B1

  公开（公告）日：2004-12-07

  Disclosed are novel compounds, compositions, and methods that are particularly useful in photodynamic therapy. In particular, the inventive compounds, compositions, and methods relate to the formation of cytotoxic radical species in the presence of light. Significantly, the compounds, compositions, and methods of the present invention do not require the presence of oxygen in the photodynamic therapy and, as such, rely on a unimolecular mechanism for producing the radicals. The inventive compounds, compositions, and methods can be used, for example, in the treatment of cancers as well as infections caused by microorganisms such as protozoa, fungi, bacteria, and viruses.

  揭示了一种在光动力疗法中特别有用的新化合物、组合物和方法。具体来说，这些创新化合物、组合物和方法涉及在光的存在下形成细胞毒性自由基物质。值得注意的是，本发明的化合物、组合物和方法在光动力疗法中不需要氧气的存在，因此依赖于产生自由基的单分子机制。这些创新的化合物、组合物和方法可以用于治疗癌症以及由原生动物、真菌、细菌和病毒引起的感染。
• Thermal reactivities of isostructural d10 metalloenediynes: metal-dependent Bergman cyclization
  作者：Elbert W. Schmitt、John C. Huffman、Jeffrey M. Zaleski

  DOI：10.1039/b008337m

  日期：——

  Isostructural d10 metalloenediynes of Cu(I), Pd(0) and Ag(I) exhibit metal-dependent variations in their thermal Bergman cyclization temperatures which correlate with differences in their alkyne termini separations.
• US6828439B1
  申请人：——

  公开号：US6828439B1

  公开（公告）日：2004-12-07
• [EN] COMPOUNDS, COMPOSITIONS, AND METHODS FOR PHOTODYNAMIC THERAPY<br/>[FR] COMPOSES, COMPOSITIONS ET PROCEDES POUR LA THERAPIE PHOTODYNAMIQUE
  申请人：ADVANCED RES & TECH INST

  公开号：WO2000050117A2

  公开（公告）日：2000-08-31

  Disclosed are novel compounds, compositions, and methods that are particularly useful in photodynamic therapy. In particular, the inventive compounds, compositions, and methods relate to the formation of cytotoxic radical species in the presence of light. Significantly, the compounds, compositions, and methods of the present invention do not require the presence of oxygen in the photodynamic therapy and, as such, rely on a unimolecular mechanism for producing the radicals. The inventive compounds, compositions, and methods can be used, for example, in the treatment of cancers as well as infections caused by microorganisms such as protozoa, fungi, bacteria, and viruses.