N,N',N''-tris(4-methylphenyl)guanidine | 47459-89-2

• 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: N,N',N''-tris(4-methylphenyl)guanidine
• 英文别名: 1,2,3-tri-p-tolylguanidine；N,N',N''-Tri-p-tolyl-guanidin；Guanidine, 1,2,3-tri(4-methylphenyl)-；1,2,3-tris(4-methylphenyl)guanidine
• CAS: 47459-89-2
• 化学式: C₂₂H₂₃N₃
• 分子量: 329.445
• InChiKey: VHULDBQGXDJTFU-UHFFFAOYSA-N

物化性质

• 熔点：
  125 °C
• 沸点：
  478.6±55.0 °C(Predicted)
• 密度：
  1.05±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.4
• 重原子数：
  25
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  36.4
• 氢给体数：
  2
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  N,N',N''-tris(4-methylphenyl)guanidine 以 乙醇 、 二氯甲烷 、 水 为溶剂， 反应 18.0h， 生成
  参考文献：
  名称：

  Six-membered [C,N] cyclopalladated sym N,N′,N″-tri(4-tolyl)guanidines: Synthesis, reactivity studies and structural aspects

  摘要：

  Six-membered [C,N] cyclopalladated sym N,N',N ''-tri(4-tolyl)guanidines, [(ArNH)(2)C=NAr] (sym = symmetrical; Ar = 4-MeC6H4; LH24-tolyl) of the types [(C,N)Pd(mu-OC(O)R)](2) (1 and 2), [(C,N)Pd(mu-Br)](2) (3), cis-[(C,N)PdLBr] (4-7), and [(C,N)Pd(acac)] (8) were prepared in high yield by established methods with a view aimed at understanding the influence of the 4-tolyl substituent of the guanidine moiety upon the solution behaviour of 1-8. The composition of 1-8 was confirmed by elemental analysis, IR, and NMR spectroscopy, and mass spectrometry. The molecular structures of 1-6 were determined by single-crystal X-ray diffraction. Palladacycles 1-3 exist as a dimer in transoid conformation in the solid state while 4-6 exist as a monomer with cis configuration around the palladium atom as the Lewis base is placed cis to the Pd-C bond due to antisymbiosis. The NMR spectra of 1-8 revealed the presence of a single isomer in solution and this spectral feature is ascribed to the rapid inversion of the six-membered "[C,N]Pd" ring due to the presence of sterically less hindered and more symmetrical 4-tolyl substituent in the =NAr unit of the guanidine moiety. (C) 2013 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2013.05.030
• 作为产物：
  描述：

  4-甲苯基异腈 在 氯仿 、 氯 作用下， 生成 N,N',N''-tris(4-methylphenyl)guanidine
  参考文献：
  名称：

  Nef, Justus Liebigs Annalen der Chemie, 1892, vol. 270, p. 281

  摘要：

  DOI：

文献信息

• Synthesis and conformational features of sym N,N′,N″-triarylguanidines
  作者：Kanniyappan Gopi、Brijesh Rathi、Natesan Thirupathi

  DOI：10.1007/s12039-010-0017-8

  日期：2010.3

  A one pot reaction involving sym N,N′-diarylthiourea and the respective arylamine in the presence of aq. KOH in nitrobenzene at ≥105°C afforded sym N,N′,N″-triarylguanidine in fair to good yield and the products have been characterized. Sym N,N′,N″-tri(4-tolyl)guanidine possesses (7) anti-anti conformation, sym N,N′,N″-tri(2-tolyl)guanidine (8) and sym N,N’,N″-tris(2,4-xylyl)guanidine (11) each possess anti-anti αβα conformation whereas sym N,N′,N″-tris(2-anisyl)guanidine possesses (9) syn-anti αββ conformation as determined by single crystal X-ray diffraction data. The observed conformations appear to result from a subtle balance between steric factor associated with the aryl substituent and multiple electronic factors namely n-π conjugation/negative hyperconjugation and non-covalent interactions in the crystal lattice.

  在一锅反应中，以水合KOH为催化剂，在硝基苯中于≥105°C下，使对称N,N'-二芳基硫脲与相应的芳香胺反应，得到了产率尚可至良好的对称N,N',N"-三芳基胍。产物已经过表征。通过单晶X射线衍射数据确定，对称N,N',N"-三(4-甲苯基)胍具有反-反构型，对称N,N',N"-三(2-甲苯基)胍和N,N',N"-三(2,4-二甲苯基)胍分别具有反-反αβα构型，而对称N,N',N"-三(2-甲氧苯基)胍则具有顺-反αββ构型。这些构型的形成似乎是芳基取代基的立体因素与多个电子因素（包括n-π共轭/负超共轭以及晶格中的非共价相互作用）之间微妙平衡的结果。
• Lewis base-catalyzed double nucleophilic substitution reaction of N -tosylaziridinofullerene with thioureas or guanidines
  作者：Qi Meng、Jun-Yu Cheng、Chun-Bao Miao、Xiao-Qiang Sun、Hai-Tao Yang

  DOI：10.1016/j.tetlet.2017.05.048

  日期：2017.6

  double nucleophilic substitution reaction of N-tosylaziridinofullerene with thioureas or guanidines affords the fullerothiazolidin-2-imine or fulleroimidazolidin-2-imine derivatives, respectively. In the case of unsymmetrical thioureas connecting an alkyl and an aryl group on each of the nitrogen atom, the transformation exhibits excellent chemoselectivity with only the aryl substituted nitrogen atom bonding

  Lewis碱催化的N-甲苯磺酰基叠氮富勒烯与硫脲或胍的双亲核取代反应分别得到了Fullerothiazolidin-2-imine或fulleroimidazolidin-2-imine衍生物。在每个氮原子上连接烷基和芳基的不对称硫脲的情况下，仅芳基取代的氮原子键合至C 60上，该转化表现出优异的化学选择性。生成的三-4-甲氧基苯基取代的全咪唑啉-2-亚胺与CS 2平滑反应，生成二-4-甲氧基苯基的全咪唑啉-2-硫酮。
• Highly Atom Efficient Guanylation of both Aromatic and Secondary Amines Catalyzed by Simple Lanthanide Amides
  作者：Qinghai Li、Shaowu Wang、Shuangliu Zhou、Gaosheng Yang、Xiancui Zhu、Yuyu Liu

  DOI：10.1021/jo0709089

  日期：2007.8.31

  It is demonstrated that the cyclopentadienyl-free simple lanthanide amides [(Me3Si)2N]3Ln(μ-Cl)Li(THF)3 (Ln = La, Sm, Eu, Y, Yb) and Ln[N(SiMe3)2]3 (Ln = Y, Yb) are highly efficient catalysts for the guanylation of both aromatic and secondary amines with a high activity under mild conditions. It is found that these catalysts are compatible with a wide range of solvents and substrates.

  结果表明，不含环戊二烯基的简单镧系酰胺[（Me 3 Si）2 N] 3 Ln（μ-Cl）Li（THF）3（Ln = La，Sm，Eu，Y，Yb）和Ln [N（ SiMe 3）2 ] 3（Ln = Y，Yb）是高效的催化剂，用于在温和条件下以高活性对芳族胺和仲胺进行鸟嘌呤化。发现这些催化剂与多种溶剂和底物相容。
• Heterocumulene Metathesis by Iridium Guanidinate and Ureylene Complexes:  Catalysis Involving Reversible Insertion To Form Six-Membered Metallacycles
  作者：Andrew W. Holland、Robert G. Bergman

  DOI：10.1021/ja026178y

  日期：2002.8.1

  The four-membered metallacycles Cp*Ir((NAr)2C=Z) have been prepared for Z = NAr and Z = O. These complexes undergo facile exchange with free heterocumulenes. This exchange process can be employed to effect the rapid, catalytic metathesis of aryl carbodiimides at room temperature and the metathesis of aryl carbodiimides with aryl isocyanates at slightly elevated temperature. The exchange process appears

  四元金属环 Cp*Ir((NAr)2C=Z) 已被制备为 Z = NAr 和 Z = O。这些配合物与游离的杂枯烯进行了轻松的交换。该交换过程可用于在室温下实现芳基碳二亚胺的快速催化复分解，以及在稍微升高的温度下实现芳基碳二亚胺与异氰酸芳基酯的复分解。交换过程似乎是通过一种新的缔合机制进行的，该机制涉及环扩张以形成六元金属环，而不是环还原以产生亚氨基配合物。对关键中间体的观察和交叉实验的结果支持了这一假设。
• A General and Mild Copper(I)-Catalyzed Three-Component Reaction of Cyanamides, Amines, and Diaryl­iodonium Triflates
  作者：Jihui Li、Hongxing Wang、Yifeng Hou、Weiguang Yu、Shuying Xu、Yucang Zhang

  DOI：10.1002/ejoc.201600332

  日期：2016.5

  three-component reaction of cyanamides, amines, and diaryliodonium triflates was developed for the synthesis of guanidines. The mild reaction accommodates both aromatic and aliphatic amines and provides the products in good yields with good functional group tolerance. Moreover, it was demonstrated that C–H activation of the arenes could be realized for the direct preparation of guanidines.

  开发了一种高效的铜催化氰胺、胺和二芳基碘三氟甲磺酸盐的三组分反应，用于合成胍。温和的反应同时容纳芳香族和脂肪族胺，并以良好的收率提供具有良好官能团耐受性的产物。此外，证明可以实现芳烃的 C-H 活化以直接制备胍。