2-bromo-N-(triphenyl-l5-phosphaneylidene)benzamide | 950921-43-4

• 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: 2-bromo-N-(triphenyl-l5-phosphaneylidene)benzamide
• 英文别名: 2-bromo-N-(triphenyl-λ5-phosphaneylidene)benzamide；Ph3P=NC(O)C6H4-2-Br；N(=PPh3)C(O)C6H4Br-2；2-bromo-N-(triphenyl-lambda5-phosphanylidene)benzamide；2-bromo-N-(triphenyl-λ5-phosphanylidene)benzamide
• CAS: 950921-43-4
• 化学式: C₂₅H₁₉BrNOP
• 分子量: 460.31
• InChiKey: HPQDPPMVMNXIGG-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

• 作为反应物：
  描述：

  2-bromo-N-(triphenyl-l5-phosphaneylidene)benzamide 在 仲丁基锂 作用下， 以 四氢呋喃 为溶剂， 反应 0.52h， 生成
  参考文献：
  名称：

  Synthesis, Structure, and Reactivity of N-Benzoyl Iminophosphoranes Ortho Lithiated at the Benzoyl Group

  摘要：

  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.

  DOI：

  10.1021/jo101151s
• 作为产物：
  描述：

  2-溴-N-羟基苯甲酰胺 在 三乙胺 、 iron(II) chloride 作用下， 以 四氢呋喃 、 乙腈 为溶剂， 反应 22.0h， 生成 2-bromo-N-(triphenyl-l5-phosphaneylidene)benzamide
  参考文献：
  名称：

  铁(II)催化膦与N-酰氧基酰胺的亚胺化构建N-酰基亚氨基正膦

  摘要：

  使用 FeCl 2作为廉价且容易获得的催化剂，描述了膦与 N-酰氧基酰胺的简便亚胺化反应，提供了具有高官能团耐受性的合成有用的N-酰基亚氨基正膦。该转化在室温下的空气气氛下很容易进行，并且可以在催化剂负载量为 1 mol% 的情况下放大至克级。产物中的亚氨基正膦基部分被进一步用作在 Rh(III) 催化下可控邻位C(sp 2 )-H 键酰胺化的有效导向基团。

  DOI：

  10.1021/acs.orglett.2c01238

文献信息

• Organogold(III) Iminophosphorane Complexes as Efficient Catalysts in the Addition of 2-Methylfuran and Electron-Rich Arenes to Methyl Vinyl Ketone
  作者：David Aguilar、María Contel、Rafael Navarro、Esteban P. Urriolabeitia

  DOI：10.1021/om700453s

  日期：2007.8.1

  14) have been found to be the more effective in both the presence and absence of silver salts. With acid-sensitive electron-rich arenes the catalytic activity of these cycloaurated complexes outperformed that of the AuCl3 salt. The synthesis and characterization of new iminophosphorane coordination and organogold(III) compounds are provided along with the results for the catalytic studies.

  在2-甲基呋喃和一些富电子芳烃与甲基乙烯基酮的加成反应中，已评估了含有C，N-钳位配体的环化化合物作为预催化剂。在银盐存在下，所有络合物均显示出与Au（I）络合物相当的催化活性。含有膦亚胺配体（R的化合物3 P NR'）为C，N-骨架如[金κ 2 -C，NC 6 H ^ 4（PPH 2 Ñ（C 6 H ^ 4 X）-2}氯2 ]（X = H，13； X = Me，14已经发现，在存在和不存在银盐的情况下，）都更有效。使用酸敏感的富电子芳烃，这些环链配合物的催化活性优于AuCl 3盐。提供了新的亚氨基正膦配位化合物和有机金（III）化合物的合成和表征，以及用于催化研究的结果。
• 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。
• Construction of <i>N</i>-Acyliminophosphoranes via Iron(II)-Catalyzed Imidization of Phosphines with <i>N</i>-Acyloxyamides
  作者：Sen Lin、Bo Lin、Zongtao Zhang、Jianhui Chen、Yanshu Luo、Yuanzhi Xia

  DOI：10.1021/acs.orglett.2c01238

  日期：2022.5.6

  Employing FeCl2 as a cheap and readily available catalyst, a facile imidization of phosphines with N-acyloxyamides is described, affording synthetically useful N-acyliminophosphoranes with high functional group tolerance. The transformation is easily performed under an air atmosphere at room temperature and could be scaled up to gram scale with a catalyst loading of 1 mol %. The iminophosphoranyl moiety

  使用 FeCl 2作为廉价且容易获得的催化剂，描述了膦与 N-酰氧基酰胺的简便亚胺化反应，提供了具有高官能团耐受性的合成有用的N-酰基亚氨基正膦。该转化在室温下的空气气氛下很容易进行，并且可以在催化剂负载量为 1 mol% 的情况下放大至克级。产物中的亚氨基正膦基部分被进一步用作在 Rh(III) 催化下可控邻位C(sp 2 )-H 键酰胺化的有效导向基团。
• 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.