N’,N’’,N’’’,N’’’’-四苄基环烯 | 18084-64-5

• 物质功能分类: 医药中间体
• 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’,N’’,N’’’,N’’’’-四苄基环烯
• 中文别名: N',N'',N''',N''''-四苄基环烯；1,4,7,10-四苄基-1,4,7,10-四氮杂环十二烷；1,4,7,1-四苄基-1,4,7,1-四氮杂环十二烷；TACD
• 英文名称: 1,4,7,10-tetrabenzyl-1,4,7,10-tetraazacyclododecane
• 英文别名: 1,4,7,10-Tetrabenzyl-1,4,7,10-tetraaza-cyclododecan；1,4,7,10-tetrabenzyl-1,4,7,10-tetrazacyclododecane
• CAS: 18084-64-5
• 化学式: C₃₆H₄₄N₄
• 分子量: 532.772
• InChiKey: VXOJKUWHCFFUCO-UHFFFAOYSA-N

物化性质

• 熔点：
  140-142 ºC
• 沸点：
  639.2±50.0 °C(Predicted)
• 密度：
  1.086
• LogP：
  2 at 20℃

计算性质

• 辛醇/水分配系数(LogP)：
  6.1
• 重原子数：
  40
• 可旋转键数：
  8
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  13
• 氢给体数：
  0
• 氢受体数：
  4

制备方法与用途

用途

1,4,7,10-四苄基-1,4,7,10-四氮杂环十二烷主要用于医药中间体。

反应信息

• 作为反应物：
  描述：

  N’,N’’,N’’’,N’’’’-四苄基环烯 在 zinc perchlorate 作用下， 以 氯仿 、 水 为溶剂， 生成
  参考文献：
  名称：

  Exciplex formation as an approach to selective Copper(II) fluorescent sensors

  摘要：

  The fluorescence of TB-cyclen (1,4,7,10-tetrabenzyl-1,4,7,10-tetraaza-cyclododecane) and its complexes with Cu-II,Cd-II, Pb-II, Zn-II, Hg-II and Ag-I are reported in 50% (v/v) CH3OH/H2O. It appears, as supported by NMR studies, that the TB-cyclen undergoes slow protonation reactions in CH3CN with 0.01 M HClO4 present. The nonprotonated TB-cyclen adopts the + + - - conformer that is sterically shielded from protonation and complex-formation, and the slow formation of the protonated forms of the ligand, and formation of the + + + + conformer, is required before complex-formation can occur. Strong emissions at 352 nm are oberved on formation of TB-cyclen complexes with Cu-II, Cd-II, Pb-II, but not with Zn-II( ), Hg (II) and Ag-I: it is suggested that these are exciplex emissions. The selectivity of the fluorescence of Cu(II)( )with TB-cyclen compared to Zn-II suggests that ligands of this type might be useful in sensing Cu(II )in neural tissue, as in the case of studying Alzheimer's disease, where potentially interefering metal ions such as Cd-II or Pb-II should not be present. The structure of [Pb(TB-cyclen)] (ClO4)(2) is reported, which shows that Pb center dot center dot center dot C pi contacts are formed to all four N-benzyl groups. Structures of [Cd (TB-cyclen)CH3CN](ClO4)(2) and [Hg(TB-cyclen)CH3CN](ClO4)(2) are reported, that show M center dot center dot center dot C pi contacts to only two of the N-benzyl groups, but the non-formation of four pi contacts may be due to the presence of coordinated CH3CN molecules. The structure of [TB-cyclenfl] ClO4 shows that the cyclen moeity of the ligand has the + + + + conformer required for complex-formation with metal ions. It is suggested that in the protonated forms of the free ligand, the + + + + conformer is stabilized with the N-benzyl groups in an upright position by the formation of N-H center dot center dot center dot C pi contacts, and C-H center dot center dot center dot C pi contacts between the upright N-benzyl groups. DFT calculations are carried out that show the structure of the exciplex that can be formed in the free (non-protonated) form of DB-cyclen, and show that its + + - - conformer is the lowest energy form.

  DOI：

  10.1016/j.ica.2020.119544
• 作为产物：
  描述：

  2-[Benzyl-[2-[benzyl-[2-[benzyl-[2-(benzylamino)acetyl]amino]acetyl]amino]acetyl]amino]acetic acid 在 硼烷四氢呋喃络合物 、 N,N-二异丙基乙胺 、 Methanaminium,N-[(dimethylamino)(3H-1,2,3-triazolo[4,5-b]pyridin-3-yloxy)methylene]-N-methyl-, hexafluorophosphate(1-) 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 45.0h， 生成 N’,N’’,N’’’,N’’’’-四苄基环烯
  参考文献：
  名称：

  From Cyclic Peptoids to Peraza-macrocycles: A General Reductive Approach

  摘要：

  Peraza-macrocycles form chelates of high thermodynamic and kinetic stability useful in diagnostic imaging (MRI, SPECT, PET), in coordination chemistry, and as catalysts. In this letter, we report an advantageous method to prepare these compounds via BH3-induced reduction of cyclic peptoids. Using this procedure, 10 homo- and heterosubstituted aza-coronands, with different sizes and side chains, have been synthesized from the corresponding cyclic oligoamides. Solid structures of free, protonated, and Na+ coordinated polyaza-derivatives have been disclosed by single crystal X-ray diffraction analysis.

  DOI：

  10.1021/acs.orglett.9b02668

文献信息

• Effects of ligand substituents on the single-molecule magnetic behavior of quinonoid-bridged dicobalt compounds
  作者：Xiao-Quan Zhu、Wen-Hai Cao、Shao-Dong Su、Xin-Tao Wu、Tian-Lu Sheng

  DOI：10.1039/d0dt00033g

  日期：——

  quinonoid-bridged dicobalt compounds [(N4Co)2LX](ClO4)2 (1-4) (X = H, Cl, Br and OMe; N4 = 1,4,7,10-tetrabenzyl-1,4,7,10-tetraazacyclododecane) are synthesized and well characterized. Single crystal X-ray diffraction analyses reveal that the coordination geometry of one side Co in compounds 1-4 changes from a triangular prism to distorted octahedron with a change in the bridged-ligand substituent. Magnetic measurements

  一系列醌桥联的二钴化合物[（N4Co）2LX]（ClO4）2（1-4）（X = H，Cl，Br和OMe； N4 = 1,4,7,10-四苄基1,4，合成并很好地表征了7,10-四氮杂环十二烷）。单晶X射线衍射分析表明，化合物1-4中Co的一侧的配位几何结构从三棱柱变为畸变的八面体，桥联配体取代基也发生了变化。磁测量表明化合物1和3表现出单分子磁行为。磁结构分析表明，四种化合物之间的弛豫势垒U的差异是由于分子中两个Co中心的各向异性轴的方向不同所致。
• The Oxo-Wall Remains Intact: A Tetrahedrally Distorted Co(IV)–Oxo Complex
  作者：Jindou Yang、Hai T. Dong、Mi Sook Seo、Virginia A. Larson、Yong-Min Lee、Jason Shearer、Nicolai Lehnert、Wonwoo Nam

  DOI：10.1021/jacs.1c04919

  日期：2021.10.20

  coordination geometry. Magnetic circular dichroism (MCD) spectroscopy further supports this finding. The hydrogen bond leads to an interesting polarization of the Co–oxo π-bonds, where one O(p) lone-pair is stabilized and leads to a regular Co(d) interaction, whereas the other π-bond shows an inverted ligand field. The reactivity of this complex in hydrogen atom and oxygen atom transfer reactions is discussed

  在本文中，我们报告了带有 N4-大环共配体 12-TBC (12-TBC = 1,4,7,10-四苄基的 Co(IV)-oxo 配合物的制备、光谱和理论表征以及反应性研究-1,4,7,10-四氮杂环十二烷）。基于Co(II)前体的配体和结构，[Co II (12-TBC)(CF 3 SO 3 ) 2]，有人会假设该物种对应于四方 Co(IV)-oxo 复合物，但光谱数据不支持这一观点。Co K-edge XAS 数据显示，在 -40 °C 下，在质子源存在的情况下，用碘代苯 (PhIO) 作为氧化剂处理 Co(II) 前体会导致 Co K-edge 发生明显变化，在同意形成 Co(IV) 中间体。共振拉曼 (rRaman) 光谱进一步证明了氧代基团的存在。有趣的是，该复合体的 EPR 数据显示出高度的菱形，表明结构扭曲。EXAFS 数据进一步支持了这一点。使用 DFT 计算，为这种具有配体
• A direct method for the <i>N</i>-tetraalkylation of azamacrocycles
  作者：Andrew J Counsell、Angus T Jones、Matthew H Todd、Peter J Rutledge

  DOI：10.3762/bjoc.12.239

  日期：——

  An efficient protocol for the direct synthesis of N-tetraalkylated derivatives of the azamacrocycles cyclam and cyclen has been developed, using a partially miscible aqueous–organic solvent system with propargyl bromide, benzyl bromide, and related halides. The method works most effectively when the reaction mixture is shaken, not stirred. A crystal structure of the N-tetrapropargyl cyclam derivative 1,4,8,11-tetra(prop-2-yn-1-yl)-1,4,8,11-tetraazacyclotetradecane diperchlorate is reported.

  已开发出一种高效的协议，用于直接合成环戊二胺环烷和环己二胺环烷的N-四烷基衍生物，使用部分不相溶的水-有机溶剂体系，其中包括丙炔基溴化物、苄基溴化物和相关卤化物。当反应混合物摇动而非搅拌时，该方法效果最佳。报道了N-四丙炔基环烷衍生物1,4,8,11-四(丙-2-炔-1-基)-1,4,8,11-四氮杂环十四烷二过氯酸盐的晶体结构。
• Tetrabenzylcyclen as a receptor for fluoride
  作者：Vladimir O. Gelmboldt、Eduard V. Ganin、Stepan S. Basok、Ekaterina Yu. Kulygina、Mark M. Botoshansky、Victor Ch. Kravtsov、Marina S. Fonari

  DOI：10.1039/c1ce05279a

  日期：——

  A tetraazacyclic ligand, tetrabenzylcyclen (L), was synthesized using an improved method with a higher yield by treatment of cyclen with benzylchloride in the presence of potassium carbonate. The reaction of L with an aqueous solution of fluorosilicic acid yielded a mixed-anionic salt with the composition [H3L][F][SiF6]·4H2O (1). The single crystal X-ray study revealed that the macrocyclic tri-cation essentially changes the conformation compared to the free ligand in order to tightly accommodate the fluoride inside and to keep the hexafluorosilicate anions and water molecules outside in the solid state complex.

  我们采用一种改进的方法合成了一种四氮杂环配体--四苄基环烯（L），该方法是在碳酸钾存在下用苄基氯处理环烯，从而获得了更高的产率。L 与氟硅酸水溶液反应生成了混合阴离子盐，其组成为 [H3L][F][SiF6]-4H2O（1）。单晶 X 射线研究显示，与游离配体相比，大环三阳离子基本上改变了构象，以便在固态复合物中将氟化物紧密地容纳在内部，并将六氟硅酸阴离子和水分子阻挡在外部。
• Enhancement of electrocatalytic abilities toward CO₂ reduction by tethering redox-active metal complexes to the active site
  作者：Habib Md. Ahsan、Brian K. Breedlove、Goulven Cosquer、Masahiro Yamashita

  DOI：10.1039/d1dt02318g

  日期：——

  Tethering metal complexes, like [Ru(bpy)2Cl2] (bpy = 2,2′-bipyridine), which are redox-active at low reduction potentials and have the ability to transfer electrons to another complex, to a [Ni(cyclen)]2+ electrocatalyst enhanced the reduction of CO2 to CO at low overpotentials. The [Ni(cyclen)]2+ electrocatalyst was modified by tethering redox-active metal complexes via 4-methylpyridyl linkers. The

  束缚金属配合物，如 [Ru(bpy) 2 Cl 2 ] (bpy = 2,2'-联吡啶)，它们在低还原电位下具有氧化还原活性，并且能够将电子转移到另一个配合物，到 [Ni( cyclen)] 2+电催化剂在低过电位下增强了 CO 2向 CO的还原。[Ni(cyclen)] 2+电催化剂通过4-甲基吡啶基连接体连接氧化还原活性金属配合物进行改性。CO 2与活性位点结合后，氧化还原活性金属络合物被还原。在 95 : 5 (v/v) CH 3 CN/H 2 O 中的受控电位电解 (CPE) 实验中，[([Ru]pic) 4 cyclen}NiCl]5+（的[Ru] + = 的Ru（联吡啶） 2氯} + ; PIC = 4-甲基吡啶基）可被用于减少CO 2到CO在转换频率的708秒（TOF） -1用法拉第效率（ FE) 为 80%，起始电位为 -1.60 V vs . NHE。同时，该电催化剂在