3-methyl-2,2,2,4-tetraphenyl-2λ⁵-[1,2]oxaphosphetane | 77613-61-7

• 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: 3-methyl-2,2,2,4-tetraphenyl-2λ⁵-[1,2]oxaphosphetane
• 英文别名: 3-Methyl-2,2,2,4-tetraphenyl-1,2lambda5-oxaphosphetane；3-methyl-2,2,2,4-tetraphenyl-1,2λ5-oxaphosphetane
• CAS: 77613-61-7
• 化学式: C₂₇H₂₅OP
• 分子量: 396.469
• InChiKey: CIBBGNQLHMBNPX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.4
• 重原子数：
  29
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  3-methyl-2,2,2,4-tetraphenyl-2λ⁵-[1,2]oxaphosphetane 生成 三苯基氧化膦
  参考文献：
  名称：

  Electronic Properties of Furyl Substituents at Phosphorus and Their Influence on ³¹P NMR Chemical Shifts

  摘要：

  The electronic properties of 2-furyl and 3-furyl substituents attached to phosphanes and phosphonium salts were studied by means of IR spectroscopy and experimental and computational P-31 NMR spectroscopy. The heteroaromatic systems proved to be electron withdrawing with respect to phenyl substituents. However, phosphorus atoms with attached furyl substituents are strongly shielded in NMR. The reason for this phenomenon was studied by solid state P-31 MAS NMR experiments. The chemical shift tensor was extracted, and the orientation within the molecules was determined. The tensor component sigma(33), which is effected the most by furyl systems, is oriented perpendicular to the P-C bonds of the substituents. P-furyl bonds are shorter than P-phenyl bonds. We assume therefore a lower ground-state energy of the molecules, because of the electron withdrawing properties of the 2-furyl systems. The sigma(para) component of the P-31 NMR magnetic shielding is therefore smaller, which results in an overall increase of the magnetic shielding.

  DOI：

  10.1021/ja057085u
• 作为产物：
  描述：

  乙基三苯基溴化膦 在 氨 、 sodium amide 作用下， 以 四氢呋喃 为溶剂， 生成 3-methyl-2,2,2,4-tetraphenyl-2λ⁵-[1,2]oxaphosphetane
  参考文献：
  名称：

  Low-temperature characterization of the intermediates in the Wittig reaction

  摘要：

  DOI：

  10.1021/ja00400a055

文献信息

• (<i>E</i> )-Selective Wittig Reactions between a Nonstabilized Phosphonium Ylide Bearing a Phosphastibatriptycene Skeleton and Benzaldehydes
  作者：Yosuke Uchiyama、Takemaru Ohtsuki、Rikiya Murakami、Munenori Shibata、Jun Sugimoto

  DOI：10.1002/ejoc.201601098

  日期：2017.1.3

  derivatives. These results clearly indicated that stereochemical drift occurred at those temperatures, even in reactions using nonstabilized phosphonium ylides. The stereochemical drift in the phosphastibatriptycene system occurred at a lower temperature than in the case of the triphenyl derivative, thus explaining the (E)-selective Wittig reactions between the benzaldehyde derivatives and the nonstabilized

  苯甲醛衍生物与带有磷酸酯三萜骨架的不稳定鏻叶立德之间的 Wittig 反应，被视为三齿芳基配体，在锂盐和钠盐的存在下，产生具有高选择性的 (E)-烯烃。如前所述，三苯基鏻叶立德与苯甲醛衍生物在相同条件下的反应主要提供 (Z)-烯烃。变温 (VT) 31P1H} NMR 光谱显示了两个信号，分配给顺式和反式 1,2-氧杂膦，它们在不同温度（分别为 –80 °C 和 –40 °C）下观察到在锂盐和钠盐存在的情况下，苯甲醛与带有磷酸三苯三烯骨架的不稳定鏻叶立德之间的 Wittig 反应表明，这些产物在 –40 °C 时存在平衡。另一方面，在三苯基鏻叶立德和苯甲醛之间的反应中没有清楚地观察到这种平衡，仅检测到一个信号。观察到的中间体通过分别带有 phosphastibatriptycene 骨架和三苯基膦部分的分离的 β-羟烷基鏻盐的去质子化证实为 1,2-oxaphosphetanes。在对氯苯甲醛存在下，β-羟烷基鏻盐与
• A Wittig Reaction with 2-Furyl Substituents at the Phosphorus Atom: Improved (Z) Selectivity and Isolation of a Stable Oxaphosphetane Intermediate
  作者：Marco Appel、Steffen Blaurock、Stefan Berger

  DOI：10.1002/1099-0690(200204)2002:7<1143::aid-ejoc1143>3.0.co;2-g

  日期：2002.4

  Wittig reactions with ylides bearing one, two or three 2-furyl groups directly bound to the phosphorus atom have been studied. Greatly improved (Z)-alkene selectivities of up to 98:2 could be observed if 2-furyl groups were present. Monitoring of the reactions by NMR spectroscopy revealed only oxaphosphetane intermediates, which became more stable with increasing number of 2-furyl substituents bound

  已经研究了与带有一个、两个或三个直接与磷原子结合的 2-呋喃基的叶立德的 Wittig 反应。如果存在 2-呋喃基，则可以观察到高达 98:2 的 (Z)-烯烃选择性大大提高。通过 NMR 光谱对反应的监测显示只有氧代膦烷中间体，随着与磷原子结合的 2-呋喃基取代基数量的增加，中间体变得更加稳定。Oxaphosphetane 10d 与三个呋喃基团被成功分离，并提供了晶体结构分析的结果。(© Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)
• Direct observation of oxaphosphetanes from typical Wittig reactions
  作者：E. Vedejs、K. A. J. Snoble

  DOI：10.1021/ja00798a066

  日期：1973.8
• VEDEJS E.; MEIER G. P.; SNOBLE K. A. J., J. AMER. CHEM. SOC., 1981, 103, NO 10, 2823-2831
  作者：VEDEJS E.、 MEIER G. P.、 SNOBLE K. A. J.

  DOI：——

  日期：——
• Low-temperature characterization of the intermediates in the Wittig reaction
  作者：E. Vedejs、G. P. Meier、K. A. J. Snoble

  DOI：10.1021/ja00400a055

  日期：1981.5