iminophosphorane A | 1246962-74-2

• 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: iminophosphorane A
• 英文别名: 2-iodo-N-(triphenyl-λ5-phosphaneylidene)benzamide；2-iodo-N-(triphenyl-lambda5-phosphanylidene)benzamide；2-iodo-N-(triphenyl-λ5-phosphanylidene)benzamide
• CAS: 1246962-74-2
• 化学式: C₂₅H₁₉INOP
• 分子量: 507.31
• InChiKey: ATCLOBPYBBCJPT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7
• 重原子数：
  29
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  29.4
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  1-Acetoxy-2-acetyl-1,2-benzjodazol-3(2H)-on 在 叠氮基三甲基硅烷 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 3.0h， 生成 iminophosphorane A
  参考文献：
  名称：

  三官能高价叠氮碘（III）试剂促进醇的后期脱羟基叠氮化

  摘要：

  我们开发了一种温和、无金属的实用方法，用于由三官能高价叠氮碘 (III) 试剂 ABZ 促进的结构复杂醇的后期脱羟基叠氮化。该反应通过S N 2 途径进行，表现出优异的化学选择性和立体特异性，并以高收率得到相应的叠氮化物。通过实验和DFT计算研究了反应机理。

  DOI：

  10.1002/chem.202200272

文献信息

• Reaction of Amide and Sodium Azide for the Synthesis of Acyl Azide, Urea, and Iminophosphorane
  作者：Devaneyan Joseph、Sunwoo Lee

  DOI：10.1021/acs.orglett.2c02429

  日期：2022.8.26

  in DMF at 25 °C and produce the symmetrical ureas in THF/H2O at 80 °C via the sequential reaction of acyl substitution and Curtius rearrangement. All acyl azides were also obtained from the secondary amides via sequential reaction of p-toluenesulfonyl chloride and NaN3. In addition, keto-stabilized iminophosphoranes were prepared from a one-pot reaction of amides, NaN3, and phosphines.

  酰胺与 NaN 3在 25 °C 下在 DMF 中反应生成酰基叠氮化物，并在 80 °C 下通过酰基取代和 Curtius 重排的顺序反应在 THF/H 2 O 中生成对称脲。所有的酰基叠氮化物也是由仲酰胺通过对甲苯磺酰氯和NaN 3 的顺序反应得到的。此外，由酰胺、NaN 3和膦的一锅法反应制备了酮基稳定的亚氨基正膦。
• Synthesis, Structure, and Reactivity of <i>N</i>-Benzoyl Iminophosphoranes <i>Ortho</i> Lithiated at the Benzoyl Group
  作者：David Aguilar、Ignacio Fernández、Luciano Cuesta、Víctor Yañez-Rodríguez、Tatiana Soler、Rafael Navarro、Esteban P. Urriolabeitia、Fernando López Ortiz

  DOI：10.1021/jo101151s

  日期：2010.10.1

  Ortho lithiation of N-benzamido-P,P,P-triaryliminophosphoranes through deprotonation with alkyllithium bases was achieved with ortho-C=O and ortho-P=N chemoselectivity. However, the synthetic scope of these processes was rather limited. Ortho-lithiated N-benzamido-P,P,P-triphenyl-iminophosphorane 8 was efficiently prepared via lithium/halogen exchange of the corresponding ortho-brominated precursor with s-BuLi in THF at -90 degrees C. The reaction of 8 with a variety of electrophiles provides an easy and mild method for the regioselective synthesis of ortho-modified iminophosphoranes via C-C (alkylation and hydroxyalkylation) and C-X (X = I, Si, P, Sn, and Hg) bond-forming reactions. NMR characterization of 8 in THF solution showed that 8 exists as an equilibrium mixture of one monomer and two dimers. The Li atoms of these species become members of five-membered rings through chelation by the ortho-metalated carbon and the carbonyl oxygen. The dimers differ in the relative orientation of the two chelates with respect to the plane defined by the C,Li, core. The equilibrium between all species is established by splitting the dimers into monomers and subsequent recombination with formation of a different dimer.