tris(p-cyanophenyl)phosphine oxide | 22836-23-3

• 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: tris(p-cyanophenyl)phosphine oxide
• 英文别名: tris(4-cyanophenyl)phosphine oxide；Tris-(p-cyan-phenyl)-phosphinoxid；C21H12N3OP；4-bis(4-cyanophenyl)phosphorylbenzonitrile
• CAS: 22836-23-3
• 化学式: C₂₁H₁₂N₃OP
• 分子量: 353.32
• InChiKey: WPKYHQBFRMSCHL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  26
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  88.4
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  tris(p-cyanophenyl)phosphine oxide 在 三氯硅烷 作用下， 以 苯 为溶剂， 反应 24.0h， 以58%的产率得到4,4',4''-phosphanetriyltribenzonitrile
  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：

  4,4,4-phosphoryltribenzoic acid 在 吡啶 、 氯化亚砜 、 氨 、 三氯氧磷 作用下， 以 苯 为溶剂， 反应 8.0h， 生成 tris(p-cyanophenyl)phosphine oxide
  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

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。
• Photooxidation of triarylphosphines under aerobic conditions in the presence of a gold(<scp>iii</scp>) complex on cellulose extracted from <i>Carthamus tinctorius</i> immobilized on nanofibrous phosphosilicate
  作者：Seyed Mohsen Sadeghzadeh、Rahele Zhiani

  DOI：10.1039/c8ra09721f

  日期：——

  Triarylphosphines were converted to the corresponding oxides via photooxidation as a novel method. In this study, cellulose was extracted from the Carthamus tinctorius plant and then oxidized by sodium metaperiodate. A gold complex was supported on this natural cellulose. Then, a gold complex on natural cellulose supported on FPS (FPS/Au(III)) was synthesized for the reduction of phosphine oxides to

  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。
• 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。
• ORGANIC ELECTROLUMINESCENCE ELEMENT
  申请人：Satou Tasuku

  公开号：US20080241518A1

  公开（公告）日：2008-10-02

  An organic electroluminescence element having at least one organic layer including a light-emitting layer between a pair of electrodes, wherein the organic electroluminescence element has an electron transport layer containing a phosphine oxide compound and an electron transport layer that does not substantially contain the phosphine oxide compound between the light-emitting layer and a cathode, the electron transport layer containing the phosphine oxide compound is nearer to the cathode, and the electron transport layer that does not substantially contain the phosphine oxide compound is nearer to the light-emitting layer. An organic EL element that exhibits high light-emission efficiency and is excellent in drive durability is provided.
• US4044060A
  申请人：——

  公开号：US4044060A

  公开（公告）日：1977-08-23