trisphosphine oxide | 809-44-9

• 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: trisphosphine oxide
• 英文别名: tris(4-(methoxycarbonyl)phenyl)phosphine oxide；tris(4-carbomethoxyphenyl)phosphine oxide；4,4',4''-phosphoryl-tri-benzoic acid trimethyl ester；4,4',4''-Phosphoryl-tri-benzoesaeure-trimethylester；tris-p-carbomethoxyphenylphosphine oxide；Tris-<4-Methoxycarbonyl-phenyl>-phosphinoxyd；Trimethyl 4,4',4''-phosphoryltribenzoate；methyl 4-bis(4-methoxycarbonylphenyl)phosphorylbenzoate
• CAS: 809-44-9
• 化学式: C₂₄H₂₁O₇P
• 分子量: 452.4
• InChiKey: QECUTBRWVVPITM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  32
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  96
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  trisphosphine oxide 在 三氯硅烷 作用下， 以 苯 为溶剂， 反应 24.0h， 以55%的产率得到trisphosphine
  参考文献：
  名称：

  N-phenyl-P,P,P-triarylphospha-.lambda.5-azenes, triarylphosphines, and triarylphosphine oxides. Substituent effects on nitrogen-15, phosphorus-31, and carbon-13 NMR spectra

  摘要：

  The syntheses and N-15, P-31, and C-13 NMR spectra of a series of N-phenyl-P,P,P-triarylphospha-lambda-5-azenes 4 and the P-31 and C-13 NMR spectra of the corresponding series of triarylphosphines 5 and triarylphosphine oxides 6 are reported. The substituent effects on the chemical shifts can be best accommodated and rationalized by use of a model for system 4 whereby the dipole of the aryl group and its pendant R group polarizes the rest of the molecule. This includes the P and N atoms and phenyl ring, where an electron-withdrawing R group increases the electron density on the P, N, and ipso C-1 while decreasing the electron density on C-3 and C-4 of the N-phenyl ring (Figure 3). A similar polarization pattern for the phosphine oxide series 6 is suggested. In the phosphine series 5, the chemical shift data is consistent with the lone electron pair on the phosphorus atom delocalizing into the aryl rings. The coupling constant data, in particular 1J(PN) for series 4 and 1J(PC) for series 4-6, were examined with use of the Hammett monosubstituent parameter (MSP) and the Taft dual-substituent parameter (DSP) approaches. For systems 4 and 6, without a lone electron pair on the phosphorus atom, a better electron-donating substituent increases the one-bond P-C(Ar) coupling constant. On the contrary, in the phosphine series 5, where there is a lone electron pair on the phosphorus, a better electron-withdrawing substituent increases the one-bond P-C(Ar) coupling constant. DSP treatment of 1J(PC), and comparing to the few related systems in the literature, shows three types of systems. One, which includes 4 and 6, has an atom, phosphorus in these cases, that does not have a lone pair of electrons attached to the ring to which is attached an atom with a lone pair of electrons. Here, the resonance effect on 1J(PC) predominates. A second series, which includes phosphines 5, has a lone pair on the atom attached to the aryl ring. In these cases, the resonance effect is approximately 50% greater than the inductive effect. Finally, the third series, exemplified by two examples from the literature, has a tetrahedral atom (without a lone pair) attached to the aryl ring and this in turn is attached to tetrahedral atoms without lone electron pairs. In these case, the resonance and inductive effects are fairly comparable.

  DOI：

  10.1021/jo00008a036
• 作为产物：
  描述：

  trisphosphine 在 gold(III) complex supported on cellulose extracted from Carthamus tinctorius immobilized on nanofibrous phosphosilicate 、 air 作用下， 反应 1.0h， 以97%的产率得到trisphosphine oxide
  参考文献：
  名称：

  三芳基膦在有氧条件下在从红花提取的固定在纳米纤维磷硅酸盐上的纤维素上的金（iii）络合物存在下的光氧化

  摘要：

  作为一种新方法，三芳基膦通过光氧化转化为相应的氧化物。在这项研究中，纤维素是从红花植物中提取的，然后被偏高碘酸钠氧化。在这种天然纤维素上支持金络合物。然后，合成了一种以 FPS 为载体的天然纤维素上的金络合物 (FPS/Au( III ))，用于将氧化膦还原为具有显着化学选择性的相应膦。FPS的形态导致更高的催化活性。使用 TEM、FESEM、FTIR、TGA 和 BET 彻底表征了FPS/Au( III ) NP。

  DOI：

  10.1039/c8ra09721f

文献信息

• Visible light-induced 4-phenylthioxanthone-catalyzed aerobic oxidation of triarylphosphines
  作者：Aishun Ding、Shijie Li、Yang Chen、Ruiwen Jin、Cong Ye、Jianhua Hu、Hao Guo

  DOI：10.1016/j.tetlet.2018.09.031

  日期：2018.10

  We report herein a visible light-induced oxidation of triarylphosphines under aerobic condition with excellent functional group tolerance. In this transformation, the photo catalyst 4-phenylthioxanthone acted as a photosensitizer for the in situ generation of singlet oxygen. This new approach provided a cheaper and greener method for the preparation of phosphine oxide, showing great advantages in environmental

  我们在此报告了在有氧条件下具有出色的官能团耐受性的可见光诱导的三芳基膦的氧化。在该转化中，光催化剂4-苯基噻吨酮用作用于原位产生单线态氧的光敏剂。这种新方法为制备氧化膦提供了一种更便宜，更环保的方法，在环境规程中显示出巨大的优势。
• Palladium-catalyzed coupling reactions of bromo-substituted phenylphosphine oxides: a facile route to functionalized arylphosphine ligands
  作者：Lijin Xu、Jun Mo、Colin Baillie、Jianliang Xiao

  DOI：10.1016/s0022-328x(03)00663-6

  日期：2003.12

  The Heck reaction of OPPh3−n(4-C6H4Br)n (n=1–3) with electron deficient and neutral olefins led to linear olefin-substituted phenylphosphine oxides, whilst the reaction with an electron rich olefin in an ionic liquid solvent resulted in the formation of acetyl variants. The same bromophenylphosphine oxides also reacted with arylboronic acids under normal Suzuki coupling conditions, affording arylated

  OPPh的Heck反应3- Ñ（4-C 6 H ^ 4溴）ñ（ñ = 1-3）与缺电子，并导致直链烯烃取代的苯基膦氧化物中性烯烃，同时用在电子富含烯烃的反应离子液体溶剂导致乙酰基变体的形成。在正常的铃木偶合条件下，相同的溴代苯基膦氧化物也与芳基硼酸反应，从而以优异的收率提供芳基化的苯基膦氧化物。还显示通过钯催化的溴化苯基膦氧化物的胺化和甲氧基羰基化是可行的。鉴于游离膦可以很容易地从氧化膦中衍生出来，钯催化的OPR 3-偶联n（C 6 H 4 Br） n（R =烷基，芳基）应该为官能化的膦配体提供一种简单而通用的途径。
• Eosin Y-catalyzed photooxidation of triarylphosphines under visible light irradiation and aerobic conditions
  作者：Yanbin Zhang、Cong Ye、Shijie Li、Aishun Ding、Guangxin Gu、Hao Guo

  DOI：10.1039/c6ra25469a

  日期：——

  A novel method for Eosin Y-catalyzed photooxidation of triarylphosphines under visible light irradiation and aerobic conditions was reported.

  报道了一种新的方法，利用Eosin Y作为催化剂，在可见光照射和氧气存在的条件下，对三芳基膦进行光氧化反应。
• Derivatized gold clusters and antibody-gold cluster conjugates
  申请人：Associated Universities, Inc.

  公开号：US05360895A1

  公开（公告）日：1994-11-01

  Antibody- or antibody fragment-gold cluster conjugates are shown wherein the conjugate size can be as small as 5.0 nm. Methods and reagents are disclosed in which antibodies, Fab' or F(ab').sub.2 fragments thereof are covalently bound to a stable cluster of gold atoms. The gold clusters may contain 6, 8, 9, 11, 13, 55 or 67 gold atoms in their inner core. The clusters may also contain radioactive gold. The antibody-cluster conjugates are useful in electron microscopy applications as well as in clinical applications that include imaging, diagnosis and therapy.

  本文介绍了抗体-或抗体片段-金簇共轭物，其中共轭物的尺寸可以小至5.0纳米。公开了一种方法和试剂，其中抗体、Fab'或F(ab')2片段被共价结合到稳定的金原子簇上。这些金簇可能包含6、8、9、11、13、55或67个金原子在它们的内核中。这些簇也可能含有放射性金。抗体-簇共轭物在电子显微镜应用以及包括成像、诊断和治疗的临床应用中非常有用。
• Rowley, Alan G.; Steedman, John R. F., Journal of the Chemical Society. Perkin transactions II, 1983, p. 1113 - 1120
  作者：Rowley, Alan G.、Steedman, John R. F.

  DOI：——

  日期：——