N,N'-bis(2-isopropylphenyl)formimidamide | 1298123-73-5

• 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,N'-bis(2-isopropylphenyl)formimidamide
• 英文别名: N,N'-bis(2-isopropylphenyl)formamidine；N,N'-bis(2-propan-2-ylphenyl)methanimidamide
• CAS: 1298123-73-5
• 化学式: C₁₉H₂₄N₂
• 分子量: 280.413
• InChiKey: OKJLYQQKEYREEN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  21
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  24.4
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  N,N'-bis(2-isopropylphenyl)formimidamide 在 碳酸氢钠 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 以58%的产率得到N-hydroxy-N,N"-bis(2-isopropylphenyl)formamidine
  参考文献：
  名称：

  Facile Synthesis of Hydroxyformamidines by the N-Oxidation of Their Corresponding Formamidines

  摘要：

  用 MCPBA（间氯过氧苯甲酸）对 N,N′-二取代脒进行 N-氧化反应，可以温和、迅速且高效地制备相应的羟基脒。这一新的合成路线为制备 N,N′-二取代羟基脒提供了有吸引力的替代方案，取代经典的合成方法。研究发现，N-氧化反应的效率以及羟基甲脒的稳定性受到 N,N′-二芳基环上取代基的影响，例如，带有苯环2,6-位取代基的化合物可以获得更高的产率（高达92%）和更稳定的产品。产物通过¹H NMR、¹³C NMR、HRMS 和/或元素分析进行表征。

  DOI：

  10.1055/s-0030-1259329
• 作为产物：
  描述：

  原甲酸三乙酯 、 2-异丙基苯胺 在 溶剂黄146 作用下， 反应 3.0h， 以67%的产率得到N,N'-bis(2-isopropylphenyl)formimidamide
  参考文献：
  名称：

  骨架取代，官能化和手性咪唑啉盐的简便制备方法。

  摘要：

  已经描述了一种由甲modular与烯化氧反应制备各种骨架取代的，官能化的和手性的咪唑啉鎓盐的通用和模块化方法，与以前报道的方法相比，该方法提供了更直接的取代咪唑啉鎓盐的途径。

  DOI：

  10.1039/c1cc15609h

文献信息

• Multicomponent Synthesis of 1-Aryl 1,2,4-Triazoles
  作者：Annie Tam、Ian S. Armstrong、Thomas E. La Cruz

  DOI：10.1021/ol401428x

  日期：2013.7.19

  A multicomponent (single reactor) process for the synthesis of 1-aryl 1,2,4-triazoles was explored and developed. This transformation prepared the 1,2,4-triazole directly from anilines, amino pyridines, and pyrimidines. The reaction scope was explored with 21 different substrates, and the position of the nitrogen atoms in the newly formed ring was established by 15N labeling and NMR spectroscopy.

  探索和开发了一种用于合成1-芳基1,2,4-三唑的多组分（单反应器）工艺。该转化直接从苯胺，氨基吡啶和嘧啶制备1,2,4-三唑。用21种不同的底物探索了反应范围，并通过15 N标记和NMR光谱确定了新形成的环中氮原子的位置。
• Facile Syntheses of N-Heterocyclic Carbene Precursors through I₂ - or NIS-Promoted Amidiniumation of <i>N</i> -Alkenyl Formamidines
  作者：Jing Li、Jiajun Jiao、Caiyun Zhang、Min Shi、Jun Zhang

  DOI：10.1002/asia.201600182

  日期：2016.5.6

  We have developed I2‐ or N‐iodosuccinimide (NIS)‐mediated amidiniumation of N‐alkenyl formamidines for the syntheses of cyclic formamidinium salts, some of which could be directly used as N‐heterocyclic carbene (NHC) precursors. Treatment of iodine‐containing formamidinium salts with Al2O3 led to the formation of cyclic formamidinium salts with an unsaturated backbone. A rhodium(I) complex ligated

  我们已经开发了我2 -或ñ的碘代丁二酰亚胺（NIS）介导的amidiniumation ñ -烯基甲脒为环状甲脒的盐的合成，其中的一些可以被直接用作N-杂环卡宾（NHC）的前体。用Al 2 O 3处理含碘的甲ami盐导致形成具有不饱和主链的环状甲ami盐。通过[Rh（cod）Cl] 2（cod = 1,5-环辛二烯）与相应甲酰胺鎓盐去质子化获得的游离卡宾的反应，制备了由代表性NHC连接的铑（I）配合物。原位制备的NHC也可以与S 8反应 得到相应的硫酮。
• N,Nʹ-diarylformamidines: Solid state structural analysis and steric-induced stereochemical exchange in solution
  作者：Michael B. Pastor、Chao Feng、Yi-Ju Tsai、Amelia Watson、Qinliang Zhao

  DOI：10.1016/j.tet.2021.131995

  日期：2021.3

  X-ray crystal structures of four substituted N,Nʹ-diarylformamidines demonstrated that cyclic dimers form in solid state from two formamidines as a tautomeric pair in s-trans configuration facilitated by two hydrogen bonds. NMR studies in various deuterated solvents along with subsequent acid addition indicate that the introduction of sterically demanding substituents at the ortho position seems to

  四个取代的N，N′-二芳基甲am的X射线晶体结构表明，环状的二聚体是由两个甲am以固态形式形成的，是由两个氢键促进的s-反式构型的互变异构对。在各种氘代溶剂中进行的NMR研究以及随后的酸加成表明，在邻位引入空间要求的取代基似乎使溶液中的甲am二聚体形成不稳定，导致质子信号出现，表明稀有的S-顺式异构体。当分子在取代基上具有明显的空间位阻时，s-反式异构体与s-cis共存CDCl 3，C 6 D 6和DMSO-d 6中的异构体。溶液中异构体的分布取决于溶剂的选择，浓度以及烷基取代基的体积。酸或配位溶剂的添加稳定了s-反式异构体。
• The Relationship between Structure and Properties in Zn ^II Complexes of Bulky <i>N</i> , <i>N′</i> ‐Diarylformamidinate <i>N</i> ‐Oxides
  作者：Mihaela Cibian、Sophie Langis‐Barsetti、Janaina G. Ferreira、Garry S. Hanan

  DOI：10.1002/ejic.201501106

  日期：2016.1

  AbstractHomoleptic zinc(II) complexes (3a–3d) of the bulky N,N′‐diarylformamidinate N‐oxide ligands N‐hydroxy‐N,N′‐bis(2,6‐diisopropylphenyl)formamidine (2a), N‐hydroxy‐N,N′‐bis(2,6‐dimethylphenyl)formamidine (2b), N‐hydroxy‐N,N′‐bis(2‐isopropylphenyl)formamidine (2c) and N‐hydroxy‐N,N′‐bis(2‐biphenyl)formamidine (2d) were synthesized and characterized. Their solid‐state structures are presented together with their solution properties, as examined by NMR and UV/Vis spectroscopy, and cyclic voltammetry. Theoretical calculations [DFT and time‐dependent DFT (TD‐DFT)] were performed to assess and to rationalize the influence of ligand modification on the properties of the complexes: the highest occupied molecular orbital (HOMO), localized on the NCNO moiety, is less influenced by the substitution pattern, whereas the lowest unoccupied molecular orbital (LUMO), localized on the aryl ring with the O–N moiety, is directly affected; therefore, the optical band gap can be fine‐tuned for potential applications.
• Ligand control in nuclearity of Zn complexes supported by formamidinates
  作者：Yi-Ju Tsai、Wenfeng Lo、Qinliang Zhao

  DOI：10.1016/j.poly.2015.05.003

  日期：2015.9

  Using N,N'-diarylformamidinate (DArF) ligands containing different substituents of varying steric properties as the supporting ligands, four Zn complexes of atypical structural geometries were successfully synthesized and fully characterized. Detailed structural comparisons indicated steric hindrance of the ligands was a crucial factor in governing the geometry and nuclearity of the Zn products. DArFs with low steric hindrance to the metal centers produced two trinuclear Zn clusters (1 and 2) where all ligands were in non-symmetric coordination modes in both solid state and solution phase. DArFs with relatively bulky substituents led to the formation of bimetallic complexes 3 and 4 in a pseudo-paddle-wheel geometry where each two Zn cores were held together by two DArFs parallel to each other. This study, together with the monozinc complex HC(NDipp)(2)}(2)Zn (Dipp = 2,6-diisopropylphenyl) in the literature, indicated that an increase in the steric demands of the ligands led to a decrease in the nuclearity of the Zn formamidinate complexes. All product complexes were relatively thermally robust, but air and moisture sensitive. A tetranuclear cluster with an interstitial oxide was obtained when a small amount of oxygen content was present during the synthesis. (C) 2015 Elsevier Ltd. All rights reserved.