Tetra-P-phenyl-P,P'-octanediyl-bis-phosphine oxide | 16524-43-9

• 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: Tetra-P-phenyl-P,P'-octanediyl-bis-phosphine oxide
• 英文别名: 1,8-bis(diphenylphosphinoyl)octane；Oktamethylen-bis-diphenylphosphinoxid；[8-Diphenylphosphoryloctyl(phenyl)phosphoryl]benzene
• CAS: 16524-43-9
• 化学式: C₃₂H₃₆O₂P₂
• 分子量: 514.584
• InChiKey: YTMDGDOVLPITHJ-UHFFFAOYSA-N

物化性质

• 沸点：
  619.8±38.0 °C(Predicted)
• 密度：
  1.14±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  7.3
• 重原子数：
  36
• 可旋转键数：
  13
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  1,8-二溴辛烷 在 sodium hydroxide 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 20.0h， 生成 Tetra-P-phenyl-P,P'-octanediyl-bis-phosphine oxide
  参考文献：
  名称：

  Understanding the Structural Properties of a Homologous Series of Bis-diphenylphosphine Oxides

  摘要：

  A homologous series of bis-diphenylphosphine oxides (CH2)(2)PO(CH2)(n)PO(C6H5)(2) (with n = 2-8; denoted 2-8] have been investigated to explore the effects of a range of competing and cooperative intermolecular and intramolecular interactions on the structural properties in the solid state. The important factors influencing the structural properties include intramolecular aspects such as the conformation of the aliphatic chain and the intramolecular interaction between the two P=O dipoles in the molecule, and intermolecular aspects such as long-range electrostatic interactions (dominated by the arrangement of the P=O dipoles), C-H ... O interactions, C-H ...pi interactions and pi ...pi interactions. Compounds 3 and 5 could be crystallized only as solvate co-crystals (3.water and 5.(toluene)(2)], whereas the crystal structures of all the other compounds contain only the bis-diphenylphospkine oxide molecule. The crystal structures have been determined from single-crystal X-ray diffraction data, with the exception of 7 (which has been determined here from powder X-ray diffraction data) and 4 (which was known previously), The compounds with even n represent a systematic structural series, exhibiting characteristic, essentially linear P=O ... P=O ... P=O dipolar arrays, together with C-H ... O and C-H ...pi interactions. For the compounds with odd n, on the other hand, uniform structural behaviour is not observed across the series, although certain aspects of these crystal structures contribute in a general sense to our understanding of the structural properties of bis-diphenylphosphine oxides. Importantly, for the compounds with odd n, there is "frustration" with regard to the molecular conformation, as the preferred all-anti conformation of the aliphatic chain gives rise to an unfavourable parallel alignment of the two P=O dipoles within the molecule. Clearly the importance of avoiding a parallel alignment of the P=O dipoles becomes greater as n decreases. Local structural aspects (investigated by high-resolution solid-state P-31 NMR spectroscopy) and thermal properties of the bis-diphenylphosphine oxide materials are also reported.

  DOI：

  10.1002/1521-3765(20000703)6:13<2338::aid-chem2338>3.0.co;2-n

文献信息

• Some aliphatic diphosphonic tetrachlorides. Part II. Some reactions of diphosphonic tetrachlorides
  作者：Gennady M. Kosolapoff、Alfred D. Brown

  DOI：10.1039/j39670001789

  日期：——

  Aliphatic diphosphonic tetrachlorides and Grignard reagents containing aryl groups readily gave diphosphine dioxides, of which several are described. In a similar reaction of the tetrachlorides with Grignard reagents containing branched alkyl groups the products were not the expected diphosphine dioxides, but the products of mono-substitution at each phosphorus atom accompanied by a reduction. A similar

  含有芳基的脂肪族二膦四氯化物和格氏试剂容易得到二膦二氧化物，其中有几种已被描述。在四氯化物与含有支链烷基的格利雅试剂的类似反应中，产物不是预期的二膦二氧化物，而是在每个磷原子处单取代的产物并伴有还原。这种格氏试剂与二氯化膦的反应获得了相似的结果。研究了影响合成的含不同长度磷间桥的二膦四氯化物的影响因素。
• Modular Access to <i>meta</i>-Substituted Benzenes via Mo-Catalyzed Intermolecular Deoxygenative Benzene Formation
  作者：Yi-Zhe Yu、Jin Bai、Jia-Min Peng、Jia-Sheng Yao、Chun-Xiang Zhuo

  DOI：10.1021/jacs.3c01330

  日期：——

  The substituted benzene derivatives are essential to organic synthesis, medicinal chemistry, and material science. However, the 1,3-di- and 1,3,5-trisubstituted benzenes are far less prevalent in small-molecule drugs than other substitution patterns, likely due to the lack of robust, efficient, and convenient synthetic methods. Here, we report a Mo-catalyzed intermolecular deoxygenative benzene-forming

  取代苯衍生物对有机合成、药物化学和材料科学至关重要。然而，1,3-二-和 1,3,5-三取代苯在小分子药物中的普遍性远低于其他取代模式，这可能是由于缺乏稳健、高效和方便的合成方法。在这里，我们报告了一种 Mo 催化的分子间脱氧苯形成反应，该反应是现成的炔酮和烯丙基胺的反应。通过使用市售的钼催化剂，以高达 88% 的收率获得了多种不对称和未官能化的 1,3-二和 1,3,5-三取代苯。通过生物活性分子的合成转化、放大合成和衍生化进一步说明了该方法的合成潜力。初步的机理研究表明，这种苯形成过程可能通过钼催化的氮杂迈克尔加成/[1,5]-氢化物转移/环化/芳构化级联进行。该策略不仅为各种间位取代的苯衍生物，但也证明了钼催化在具有挑战性的分子间脱氧交叉偶联反应中的潜力。
• Turanov; Tsvetkov; Kharitonov, Russian Journal of General Chemistry, 1999, vol. 69, # 7, p. 1075 - 1080
  作者：Turanov、Tsvetkov、Kharitonov、Safronova、Yarkevich

  DOI：——

  日期：——
• US7189500B2
  申请人：——

  公开号：US7189500B2

  公开（公告）日：2007-03-13
• US7195865B2
  申请人：——

  公开号：US7195865B2

  公开（公告）日：2007-03-27