N-(三苯基-lambda~5~-磷烷亚基)苯酰胺 | 17436-52-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: N-(三苯基-lambda~5~-磷烷亚基)苯酰胺
• 英文名称: benzoyliminotriphenylphosphorane
• 英文别名: N-(triphenyl-λ⁵-phosphanylidene)benzamide；N-benzoyltriphenylphospha-λ⁵-azene；N-(triphenyl-λ5-phosphoranylidene)benzamide；N-(triphenyl-λ5-phosphanylidene)benzamide；N-(triphenylphosphoranylidene)benzamide；(Benzoylimino)triphenylphosphoran；n-(triphenyl-|E5-phosphanylidene)benzamide
• CAS: 17436-52-1
• 化学式: C₂₅H₂₀NOP
• 分子量: 381.414
• InChiKey: HXUHLJYSGJCHSG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.3
• 重原子数：
  28
• 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：

  N-(三苯基-lambda~5~-磷烷亚基)苯酰胺 在 叔丁基锂 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 生成 (2-(diphenylphosphoryl)phenyl)(phenyl)methanone
  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：

  aminotriphenylphosphonium bromide 在 正丁基锂 作用下， 以 四氢呋喃 为溶剂， 反应 16.0h， 生成 N-(三苯基-lambda~5~-磷烷亚基)苯酰胺
  参考文献：
  名称：

  L'氮杂ylure N-二lithie（C 6 H ^ 5）3 PNLi，reactif D'胺化

  摘要：

  锂化的氮杂-叶立德的制备已得到改进，并且描述了其对烷基和酰基卤的一锅反应性，以得到氨基phosph盐和相应的胺。

  DOI：

  10.1016/s0040-4039(00)80385-8

文献信息

• The Preparation of 1,2,3-Trisubstituted Guanidines
  作者：Alan R. Katritzky、Niveen M. Khashab、Sergey Bobrov

  DOI：10.1002/hlca.200590131

  日期：2005.7

  diverse amines by use of the new reagent classes (bis-benzotriazol-1-yl-methylene)amines 13a–13f and benzotriazole-1-carboxamidines 17a–17i is described. The preparation is described for a variety of both acyclic and cyclic 1,2,3-trisubstituted guanidines in high yields.

  本文介绍了一种操作简便，有效的基于苯并三唑的方法，该方法通过使用新的试剂类别（双-苯并三唑-1-基-亚甲基）胺13a - 13f和苯并三唑-1-甲17 17a - 17i来对多种胺进行胍基化。以高收率描述了用于多种无环和环状1,2,3-三取代胍的制备方法。
• Reactions of cobaltacyclopentadiene complexes with organic azides directed toward synthesis of highly substituted pyrroles
  作者：Pangbu Hong、Hiroshi Yamazaki

  DOI：10.1016/0022-328x(89)85033-8

  日期：1989.9

  respectively. The reaction of Ic with benzenesulfonyl azide gives only Vb in 57% yield. In the reaction of Id (R1  R3  Ph, R2  R4  CO2CH3) with benzenesulfonyl azide, Vb was unexpectedly obtained in 26% yield, together with 2,4-diphenyl-3,5-bis(methoxycarbonyl)pyrrole (Vc, 30%), which suggests that a skeletal rearrangement of the metallacycle IXd to IXc occurs during the reaction. The reaction of Ic or

  所述cobaltacyclopentadiene复合物的反应（η 5 -C 5 H ^ 5）（PPH 3） - [R 4）（I）与有机叠氮化物进行了研究。络合物Ia（R 1＝ R 2＝ R 3＝ R 4＝ Ph）在80℃下与叠氮化苯反应，以73％的收率得到1,2,3,4,5-五苯基吡咯。类似地，Ia与苯甲酰基和叔丁氧羰基叠氮化物的反应分别以41％和64％的收率得到1-苯甲酰基-和1-（叔丁氧羰基）-2,3,4,5-四苯基吡咯，但与p的反应-甲苯磺酰基叠氮化物分别以35和45％的产率得到2,3,4,5-四苯基吡咯和3,4,5,6-四苯基哒嗪，以取代预期的1-（对甲苯磺酰基）-2,3,4 ，5-四苯基吡咯。Ic的反应（R 1  - [R 3 博士，R 2  - [R 3 = CO 2 CH 3）与叠氮基苯在130℃下给出1,2,5-三苯基-3,4-二（甲氧基羰基）吡咯（ IIc）和2,5-二苯基-3
• Preparation and synthetic applications of iminophosphoranes derived from o-substituted arylazides: preparation of pyrazolo[1,2-b]indazole, 4H-3,1-benzoxazine and quinoline derivatives. Crystal structure of 2-[2-(4-methoxybenzoylamino)phenyl]-4-methylquinoline.
  作者：Pedro Molina、Carlota Conesa、Asunción Alías、Antonio Arques、María D. Velasco、Antonio L. Llamas-Saiz、Concepción Foces-Foces

  DOI：10.1016/s0040-4020(01)87234-3

  日期：1993.8

  dependent on the nature of the ortho-substituent. The Aza Wittig-type reaction of iminophosphorane derived from the ortho-azido acetophenone with isocyanates and aroyl chlorides leads to the previously unreported 4-methylene-4H-3,1-benzoxazine ring. The crystal and molecular structure of 2-[2-(4-methoxybenzoylamino)phenyl]-4-methylquinoline has been established by X-Ray diffraction methods.

  已经研究了几种邻位取代的芳基叠氮化物与三苯基膦的斯托丁格反应。发现反应产物强烈取决于邻位取代基的性质。衍生自邻叠氮基苯乙酮的亚氨基正膦与异氰酸酯和芳酰氯的Aza Wittig型反应可导致先前未报道的4-亚甲基-4H-3,1-苯并恶嗪环。通过X射线衍射方法建立了2- [2-（4-（甲氧基苯甲酰基氨基）苯基] -4-甲基喹啉的晶体和分子结构。
• Interweaving Visible‐Light and Iron Catalysis for Nitrene Formation and Transformation with Dioxazolones
  作者：Jing‐Jing Tang、Xiaoqiang Yu、Yi Wang、Yoshinori Yamamoto、Ming Bao

  DOI：10.1002/anie.202016234

  日期：2021.7.19

  transfer reactions with dioxazolones for intermolecular C(sp3)-N, N=S, and N=P bond formation are described. These reactions occur with exogenous-ligand-free process and feature satisfactory to excellent yields (up to 99 %), an ample substrate scope (109 examples) under mild reaction conditions. In contrast to intramolecular C−H amidations strategies, an intermolecular regioselective C−H amidation via

  本文描述了可见光驱动的铁催化氮烯转移反应与二恶唑酮分子间 C(sp 3 )-N、N=S 和 N=P 键的形成。这些反应在无外源配体的过程中发生，并且具有令人满意的优异产率（高达 99%），在温和的反应条件下具有足够的底物范围（109 个例子）。与分子内 C−H 酰胺化策略相反，设计了通过可见光诱导的氮烯转移反应的分子间区域选择性 C−H 酰胺化。机理研究表明该反应通过自由基途径进行。计算研究表明，二恶唑酮的脱羧取决于通过可见光照射将六重态二恶唑酮结合铁物质转化为四重旋态。
• Ruthenium(<scp>ii</scp>)-catalyzed C–H activation/C–N bond formation via in situ generated iminophosphorane as the directing group: construction of annulated pyridin-2(1H)-ones
  作者：Rajesh K. Arigela、Ravi Kumar、Trapti Joshi、Rohit Mahar、Bijoy Kundu

  DOI：10.1039/c4ra10105g

  日期：——

  We describe an efficient and straightforward synthesis of annulated pyridin-2(1H)-ones following condensation of acyl azides with internal alkynes via the ruthenium-catalyzed ortho C–H bond activation. The reaction in DCE proceeds via in situ generation of iminophosphoranes as directing group-coordination of Ru with N-atom-ortho cyclometallation-insertion of an alkyne into the Ru–C bond-protonation-reductive elimination in a domino sequence. The role and stability of in situ generated iminophosphorane and ruling out the possibility for the benzamide involvement was established using 1H and 31P NMR experiments.

  我们描述了一种高效且简单的合成方法，通过鲁钛催化的邻位C–H键活化，将酰基叠氮化物与内部炔烃缩合，合成环状吡啶-2(1H)-酮。该反应在DCE中进行，通过原位生成的亚胺膦烷作为指向性基团，通过鲁与N原子之间的邻位环金属化、炔烃插入Ru–C键、质子化以及还原消除等一系列多米诺反应进行。我们使用¹H和³¹P NMR实验确立了原位生成的亚胺膦烷的角色和稳定性，并排除了苯甲酰胺参与的可能性。