苯胺,N-[三(4-甲氧苯基)正膦亚基]- | 133191-98-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 苯胺,N-[三(4-甲氧苯基)正膦亚基]-
• 英文名称: N-phenyl-P,P,P-tris(p-methoxyphenyl)phospha-λ⁵-azene
• 英文别名: Tris(4-methoxyphenyl)(phenylimino)-lambda~5~-phosphane；tris(4-methoxyphenyl)-phenylimino-λ5-phosphane
• CAS: 133191-98-7
• 化学式: C₂₇H₂₆NO₃P
• 分子量: 443.482
• InChiKey: FZYSVTXWHFKABN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.4
• 重原子数：
  32
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  40
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  三(4-甲氧苯基)膦 、 苯胺 在 溴 、 三乙胺 作用下， 生成 苯胺,N-[三(4-甲氧苯基)正膦亚基]-
  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

• Kinetics and mechanism of the nitrosobenzene deoxygenation by trivalent phosphorous compounds
  作者：V. S. Khursan、V. A. Shamukaev、E. M. Chainikova、S. L. Khursan、R. L. Safiullin

  DOI：10.1007/s11172-013-0359-8

  日期：2013.11

  of aryl nitroso compounds with organic phosphines and phosphites in aerated media is a convenient non-photolytic procedure to generate aromatic nitroso oxides. The reaction rate constants and activation parameters of the key (for the proposed method of nitroso oxide generation) reaction of nitrosobenzene with tripenyl phosphite or para-substituted phosphines (4-RC6H4)3P (R = MeO, Me, H, F), as well

  芳基亚硝基化合物与有机膦和亚磷酸酯在充气介质中的反应是一种方便的非光解过程，可生成芳族亚硝基氧化物。亚硝基苯与亚磷酸三烯酯或对位取代膦 (4-RC6H4)3P (R = MeO, Me, H, F) 反应的关键（对于所提出的亚硝基氧化物生成方法）反应的反应速率常数和活化参数，如采用动力学分光光度法和化学发光法测定了对甲氧基亚硝基苯与三苯基膦在乙腈中的含量。正如在 M06L/6-311+G(d,p) 近似中使用哈米特相关分析和 DFT 计算所揭示的那样，电子密度向亚硝基化合物的显着转移发生在反应的过渡态。将电子给体取代基 MeO 引入 PhNO 的对位使亚硝基化合物的反应性降低了两个数量级。与三苯基膦相比，亚磷酸三苯酯在氧原子转移反应中的反应性低两个数量级。在 PhNO 与膦反应的情况下，表观速率常数取决于反应介质中的氧含量。