N-o-toluoyltriphenylphospha-λ⁵-azene | 95978-80-6

• 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: N-o-toluoyltriphenylphospha-λ⁵-azene
• 英文别名: 2-methyl-N-(triphenyl-l5-phosphaneylidene)benzamide；2-methyl-N-(triphenyl-λ⁵-phosphanylidene)benzamide；N(=PPh3)C(O)C6H4Me-2；Ph3P=NC(O)C6H4-2-Me；2-methyl-N-(triphenyl-lambda5-phosphanylidene)benzamide；2-methyl-N-(triphenyl-λ5-phosphanylidene)benzamide
• CAS: 95978-80-6
• 化学式: C₂₆H₂₂NOP
• 分子量: 395.441
• InChiKey: DTOMVCMNEOFUIQ-UHFFFAOYSA-N

物化性质

• 熔点：
  155-156 °C(Solv: methanol (67-56-1); water (7732-18-5))
• 沸点：
  558.3±43.0 °C(Predicted)
• 密度：
  1.10±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.7
• 重原子数：
  29
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.04
• 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：

  甲醇 、 N-o-toluoyltriphenylphospha-λ⁵-azene 在 双(乙腈)氯化钯(II) 、 Oxone 作用下， 反应 18.0h， 以61%的产率得到
  参考文献：
  名称：

  Pd-catalysed ortho-alkoxylation of benzamides N-protected with an iminophosphorane functionality

  摘要：

  Pd催化的苯甲酰胺的ortho-烷氧基化反应，以醇为底物，通过酮稳定的亚磷酰胺保护基团进行，具有区域选择性，并且能容忍不同的取代基和醇。

  DOI：

  10.1039/c5nj00189g
• 作为产物：
  描述：

  对甲苯甲酸 在 吡啶 、 草酰氯 、 盐酸羟胺 、 potassium carbonate 、 N,N-二甲基甲酰胺 、 copper(l) chloride 作用下， 以 二氯甲烷 、 氯仿 、 水 、 乙酸乙酯 为溶剂， 反应 19.5h， 生成 N-o-toluoyltriphenylphospha-λ⁵-azene
  参考文献：
  名称：

  铜 (I) 催化脱羧 N-磷酸化：使用二恶唑酮和膦模块化制备 N-酰基亚氨基正膦

  摘要：

  二恶唑酮和膦已被用于在简单的热条件下在铜(I)催化中获得N-酰基亚氨基正膦。该协议的合成实用性通过具有出色原子经济性的广泛底物得到证明。优化过程表明铜对目标转化具有催化作用。还进行了N-酰基亚氨基正膦的官能化研究。我们的反应方案与含有生物活性基序的N-酰基亚氨基正膦类似物的示例兼容。

  DOI：

  10.1002/adsc.202300693

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。
• 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 of N-acyl-, N-sulfonyl-, and N-phosphinylphospha(PV)azenes by a redox-condensation reaction using amides, triphenylphosphine, and diethyl azodicarboxylate
  作者：Shmuel Bittner、Yonit Assaf、Penina Krief、Martin Pomerantz、Barbara T. Ziemnicka、Christina G. Smith

  DOI：10.1021/jo00210a027

  日期：1985.5
• 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.
• Divergent Behavior in the Cyclopalladation of Phosphorus Ylides and Iminophosphoranes
  作者：David Aguilar、Miguel Angel Aragüés、Raquel Bielsa、Elena Serrano、Rafael Navarro、Esteban P. Urriolabeitia

  DOI：10.1021/om7002877

  日期：2007.7.1

  The cyclopalladation of the stabilized iminophosphoranes Ph3PNC(O)C6H4R (R = H 1a, 4-OMe 1b, 3-OMe 1c, 2-Me 1d, 3-Me 1e) results in the regioselective activation of the ortho CH bond of the benzamide ring, giving exo-[Pd(mu-Cl)C,N-C6H3(R)C(O)NPPh3-2}}](2) (R = H 2a, 5-OMe 2b, 4-OMe 2c, 3-Me 2d, 4-Me 2e). The palladated ligand behaves as a strong C,N-chelating group and cannot be easily displaced by other chelating ligands. This is clear from the reaction of 2c with Tl(acac), py, or AgClO4/LandL, which gives [Pd(acac)C,N-C6H3(MeO-4)C(O)NPPh3-2}}] (3c), [PdClC,N-C6H3(MeO-4)C(O)NPPh3-2}}(py)] (4c), or [PdC,N-C6H3(MeO-4)C(O)NPPh3-2}}(LandL)]ClO4 (LandL = dppe 5c, bipy 6c, phen 7c). However, Pd(OAc)(2) reacts with the ylides Ph3PCHC(O)C6H4R (R = H 8a, 3-OMe 8b, 2,5-(OMe)(2) 8c) to give the C,C-orthometalated complexes [Pd(mu-Cl)C,C-[C6H4(PPh2CHC(O)C6H4R)-2]}] (R = H 9a, 3-OMe 9b, 2,5-(OMe)(2) 9c), which are also regioselectively obtained. The C,C-metalated chelate is very stable, as shown by the reactions of 9b with Tl(acac), PPh3, and AgClO4/LandL. The X-ray structures of 2d and 9b have been determined. Unexpectedly, the reaction of Pd(OAc)(2) with the ylide [Ph3PCHC(O)C6H3-2,4-(OMe)(2)] (16) gives the polymer [(mu-Cl)PdC6H4(PPh2CH-C(O)C6H2-3,5-(OMe)(2))-2}-kappa-C,C,C,O)Pd(mu-Cl)](n) (17) as a result of a double palladation, giving two types of metalacycles: in one of them, the Pd atom is bonded to the ylidic C alpha atom and has activated an ortho C(Ph)-H bond of the PPh3 group; in the other one, the Pd atom is bonded to the carbonyl oxygen and has activated an ortho C-H bond of the C6H3(OMe)(2) unit. This tetradentate ylide ligand is remarkably stable.