ethyn-1-ylphosphine | 34627-31-1

• 分子结构分类: 有机化合物 - 乙炔化物
• 英文名称: ethyn-1-ylphosphine
• 英文别名: 1-ethynylphosphine；ethynylphosphine；Ethynylphosphin；Dicarbon phosphide；ethynylphosphane
• CAS: 34627-31-1
• 化学式: C₂H₃P
• 分子量: 58.0196
• InChiKey: LQEQXNYQQIBNEM-UHFFFAOYSA-N

物化性质

• 熔点：
  >250 °C (decomp)
• 沸点：
  31.4±23.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  3
• 可旋转键数：
  0
• 环数：
  0.0
• 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：

  ethyn-1-ylphosphine 在 三乙胺 作用下， 以 四氢呋喃 为溶剂， 生成 1-phosphapropyne
  参考文献：
  名称：

  Lewis base-induced rearrangement of primary ethyn-1-ylphosphines, a new and efficient route to phosphaalkynes

  摘要：

  通过原生乙炔-1-基膦的低温路易斯碱诱导重排，可以制备出具有原生碳取代基的磷炔；其机理涉及到一个 P 未取代的磷烯中间体。

  DOI：

  10.1039/c39920000415
• 作为产物：
  描述：

  乙炔基膦酸二异丙酯 在 dichloroalane 作用下， 生成 ethyn-1-ylphosphine
  参考文献：
  名称：

  The Gas-Phase Acidity of HCP, CH3CP, HCAs, and CH3CAs: An Unexpected Enhanced Acidity of the Methyl Group

  摘要：

  The gas-phase acidities of methylidynephosphine, HC=P. ethylidynephosphine. CH3C=P. and ethylidynearsine, CH3C=As, have been measured by means of Fourier Transform Ion Cyclotron Resonance (FTICR) mass spectrometry and calculated Lit the CCSD(T)/6-311+G(3df,2p)//QCISD/ 6-311 + G(df.p) level of theory. An analysis of these results shows that, in contrast to the well-known fact that HC=N is a stronger acid than CH3C=N, CH3C=P and CH3C=As are more acidic than HC=P and HC=As, respectively. The most important consequence of this unexpected effect is that while HC=P and HC=As are found to be weaker acids than HC=N. the opposite trend is found for the corresponding methyl derivatives, the acidity of which increases as CH3C=N < CH3C=P < CH3C=As. Also the effects of deprotonation on the structures and the vibrational frequencies of HC=X and CH3C=X (X=N, P, As) compounds are qualitatively similar. but quantitatively very different for nitrogen- as compared with phosphorus- and arsenic-containing compounds. A rationalization of these differences in terms of the bonding differences is presented.

  DOI：

  10.1002/1521-3765(20021104)8:21<4919::aid-chem4919>3.0.co;2-j

文献信息

• Gas-Phase Basicity and Acidity Trends in α,β-Unsaturated Amines, Phosphines, and Arsines
  作者：Otilia Mó、Manuel Yáñez、Michèle Decouzon、Jean-François Gal、Pierre-Charles Maria、Jean-Claude Guillemin

  DOI：10.1021/ja982657e

  日期：1999.5.1

  The acidity and basicity trends in the series of α,β-unsaturated amines, phosphines, and arsines were analyzed through the use of G2 ab initio calculations and the examination of experimental data obtained by means of FT-ICR techniques. The α,β-unsaturated amines, phosphines, and arsines are less basic but significantly more acidic than the corresponding saturated analogues. However, while both vinyl-

  通过使用 G2 ab initio 计算和检查通过 FT-ICR 技术获得的实验数据，分析了一系列 α,β-不饱和胺、膦和胂的酸度和碱度趋势。与相应的饱和类似物相比，α,β-不饱和胺、膦和胂的碱性较低，但酸性明显更强。然而，虽然乙烯基和乙炔胺都优先在 β-碳原子上质子化，但乙烯基和乙炔基膦在气相中是磷碱。胂与相应的膦非常相似，尽管 Cα 原子的质子化与杂原子的质子化竞争。由于 XH- 基团与 C-C 多重键的有利相互作用，不饱和化合物的酸性增强主要归因于阴离子的稳定化。这种稳定作用对胺类最大，对胂类最小。这些不饱和化合物的低相对碱性是由于不稳定...
• An Efficient Photochemical Route Towards Triplet Ethynylphosphinidene, HCCP
  作者：Arun‐Libertsen Lawzer、Thomas Custer、Jean‐Claude Guillemin、Robert Kołos

  DOI：10.1002/anie.202016052

  日期：2021.3.15

  While the archetypal free phosphinidene, H‐P, has been studied for over a century, reports on uncomplexed, univalent phosphorus compounds are very sparse. Here we demonstrate production of HCCP in solid argon through the UV‐induced rearrangement and subsequent dehydrogenation of phosphapropyne, CH3CP. Migration of H atoms along the CCP backbone of CH3CP resulted in production of the previously unobserved

  原型游离次膦酸酯H-P的研究已经有一个多世纪的历史了，但有关未络合的一价磷化合物的报道却很少。在这里，我们证明了通过UV诱导的重排以及随后的磷丙炔CH 3 CP的脱氢，在固态氩气中生产HCCP 。H原子沿着CH 3 CP的CCP主链迁移导致产生以前未被观察到的物质1-磷丙二烯（CH 2 = C = PH），然后是乙炔基膦（HCCPH 2）。
• Lewis base-induced rearrangement of primary ethyn-1-ylphosphines, a new and efficient route to phosphaalkynes
  作者：Jean-Claude Guillemin、Tajdine Janati、Jean-Marc Denis

  DOI：10.1039/c39920000415

  日期：——

  Phosphaalkynes bearing primary carbon substituents are prepared in good yield by low-temperature Lewis base-induced rearrangement of primary ethyn-1-ylphosphines; the mechanism involves a P-unsubstituted phosphaallene intermediate.

  通过原生乙炔-1-基膦的低温路易斯碱诱导重排，可以制备出具有原生碳取代基的磷炔；其机理涉及到一个 P 未取代的磷烯中间体。
• Synthesis, photoelectron spectroscopy and quantum chemical study of kinetically unstabilized phosphines complexed by borane
  作者：Balázs Németh、Brahim Khater、Tamás Veszprémi、Jean-Claude Guillemin

  DOI：10.1039/b823186a

  日期：——

  selective trapping in vacuo and the complexes were characterized by NMR and infrared spectroscopy and mass spectrometry. A kinetic stability lower than that of the corresponding free systems was observed. A series composed of these compounds and methyl-, vinyl-, allyl- and propargylphosphine-boranes was investigated by photoelectron spectroscopy and B3LYP/aug-cc-pVTZ quantum chemical study in order to define

  乙炔基和烯丙基膦基硼烷是通过在低温下将硼烷加到游离膦上来制备的。通过在真空中选择性捕集来进行纯化，并通过NMR，红外光谱法和质谱法对络合物进行表征。观察到动力学稳定性低于相应的自由体系。通过光电子能谱和B3LYP / aug-cc-pVTZ量子化学研究，研究了由这些化合物以及甲基，乙烯基，烯丙基和炔丙基膦-硼烷组成的系列，以定义自由系统与电子之间的电子效应变化。相应的复合体。尽管络合只会导致不饱和部分发生微小变化，但由于电荷从磷到硼的转移，PC键在所有情况下均会缩短。在络合物和自由体系中可以发现类似的旋转异构体，并且仅在烯丙基衍生物的情况下，相对稳定性的顺序相反。计算的络合能在80-100 kJ mol（-1）之间，与快速真空热解实验一致。在α，β-不饱和化合物的情况下，通过改变游离膦中孤电子对和π键之间的直接共轭到σ（PB）键与不饱和键的超共轭的变化，可以轻松描述光电子光谱相应的复合衍生
• Guillemin, Jean-Claude; Savignac, Philippe; Denis, Jean-Marc, Inorganic Chemistry, 1991, vol. 30, # 9, p. 2170 - 2173
  作者：Guillemin, Jean-Claude、Savignac, Philippe、Denis, Jean-Marc

  DOI：——

  日期：——