tris{[2-({2-[2-(2-methoxyethoxy)ethoxy]ethoxy}carbonyl)ethoxy]methyl}methylamine | 247941-83-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: tris{[2-({2-[2-(2-methoxyethoxy)ethoxy]ethoxy}carbonyl)ethoxy]methyl}methylamine
• 英文别名: 2-[2-(2-Methoxyethoxy)ethoxy]ethyl 3-[2-amino-3-[3-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]-3-oxopropoxy]-2-[[3-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]-3-oxopropoxy]methyl]propoxy]propanoate；2-[2-(2-methoxyethoxy)ethoxy]ethyl 3-[2-amino-3-[3-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]-3-oxopropoxy]-2-[[3-[2-[2-(2-methoxyethoxy)ethoxy]ethoxy]-3-oxopropoxy]methyl]propoxy]propanoate
• CAS: 247941-83-9
• 化学式: C₃₄H₆₅NO₁₈
• 分子量: 775.886
• InChiKey: HBLBJDIFYXCPLV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -3.1
• 重原子数：
  53
• 可旋转键数：
  45
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  216
• 氢给体数：
  1
• 氢受体数：
  19

反应信息

• 作为反应物：
  描述：

  benzyl N-tris[(2-carboxyethyloxy)methyl]methylcarbamate 、 tris{[2-({2-[2-(2-methoxyethoxy)ethoxy]ethoxy}carbonyl)ethoxy]methyl}methylamine 在 1-羟基苯并三唑 、 N,N'-二环己基碳二亚胺 作用下， 以 四氢呋喃 为溶剂， 反应 144.0h， 以58%的产率得到benzyl N-(tris{[3-oxo-3-({tris[(3-{2-[2-(2-methoxyethoxy)ethoxy]ethoxy}-3-oxopropoxy)methyl]methyl}amino)propoxy]methyl}methyl)carbamate
  参考文献：
  名称：

  具有束缚轴向配体的树突状铁卟啉：细胞色素的新模型化合物

  摘要：

  零代（[1⋅FeIII]Cl）、一个（[2⋅FeIII]Cl）和两个（[3⋅FeIII]Cl）（图1）的新型树枝状铁卟啉被制备为细胞色素模型（方案1 和 2）。它们的特点是通过拴在卟啉核心上的两个咪唑在铁中心控制轴向结扎。与核心化合物 [4·FeIII]Cl 类似，它们是六配位低自旋配合物，如 UV/VIS（图 3 和 4）和 EPR 光谱以及 Evans 对磁矩的测量所证明的 -舍福得法。还原成相应的铁 (II) 配合物后，配位环境不会改变。通过尺寸排阻色谱法纯化树枝状铁卟啉，并通过基质辅助激光解吸电离质谱法（MALDI-TOF-MS；图 5 和图 6）显示没有结构缺陷。凭借其三甘醇单甲醚表面基团，这三种树枝状模拟物可溶于极性差异很大的溶剂中。电化学研究（图 7 和图 8）和光学氧化还原滴定法（图 9）表明，在 CH2Cl2、MeCN 和 H2O 中 FeIII/FeII 对的电位强烈地移动到更正的值（高达

  DOI：

  10.1002/1522-2675(200202)85:2<571::aid-hlca571>3.0.co;2-y
• 作为产物：
  描述：

  三甘醇单甲醚 在 palladium on activated charcoal 氢气 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 20.0 ℃ 、100.0 kPa 条件下， 反应 4.5h， 生成 tris{[2-({2-[2-(2-methoxyethoxy)ethoxy]ethoxy}carbonyl)ethoxy]methyl}methylamine
  参考文献：
  名称：

  Catalytic Dendrophanes as Enzyme Mimics: Synthesis, Binding Properties, Micropolarity Effect, and Catalytic Activity of Dendritic Thiazolio-cyclophanes

  摘要：

  Catalytic dendrophanes 9 and 10 were prepared as functional mimics of the thiamine-diphosphate-dependent enzyme pyruvate oxidase, and studied as catalysts in the oxidation of naphthalene-2-carbaldehyde (4) to methyl naphthalene-2-carboxylate (8) (Scheme 1). They are composed of a thiazolio-cyclophane initiator core with four generation-2 (G-2) poly(etheramide) dendrons attached. The two dendrophanes were synthesized by a convergent growth strategy by coupling dendrons 11 and 12, respectively (Scheme 2), with (chloromethyl)-cyclophane 42 (Scheme 5) and subsequent conversion with 4-methylthiaaole (Scheme 7). The X-ray crystal structures of cyclophane precursors 30 (Scheme 3), 37 and 38 (Scheme 5) on the way to dendrophanes were determined (Fig. I). The crystal-structure analysis of the benzene clathrate of 37 revealed the formation of channel-like stacks by the cyclophane which incorporate its morpholinomethyl side chain and the enclathrated benzene molecule (Fig. 2). The interactions of the enclathrated benzene molecule with the phenyl rings of the two adjacent cyclophane molecules in the stack closely resemble those between neighboring benzene molecules in crystalline benzene (Fig. 3). The characterization by MALDI-TOF-MS (Fig. 4) and H-1- and C-13-NMR spectroscopy (Fig. 5) proved the monodispersity of the G-2 dendrophanes 9 and 10 with molecular weights up to 11500 Da (Eor 10). H-1-NMR and fluorescence binding titrations in H2O and aqueous MeOH showed that 9 and 10 form stable 1:1 complexes with naphthalene-2-carbaldehyde (4) and 6-(p-toluidino)naphthalene-2-sulfonate (48, TNS) (Tables 1 and 2). The evaluation of the fluorescence-emission maxima of bound TNS revealed that the dendritic branching creates a microenvironment of distinctly reduced polarity at the cyclophane core by limiting its exposure to bulk solvent. Initial rate studies for the oxidation of naphthalene-2-carbaldehyde to methyl naphthalene-2-carboxylate in basic aqueous MeOH in the presence of flavin derivative 6 revealed only a weak catalytic activity of dendrophanes 9 and 10 (Table 3), despite the favorable micropolarity at the cyclophane active site. The low catalytic activity in the interior of the macromolecules was explained by steric hindrance of reaction transition states by the dendritic branches.

  DOI：

  10.1002/(sici)1522-2675(19990707)82:7<1066::aid-hlca1066>3.0.co;2-o

文献信息

• Synthesis of dendritic iron(II) porphyrins with a tethered axial imidazole ligand designed as new model compounds for globins
  作者：Philipp Weyermann、François Diederich

  DOI：10.1039/b007611m

  日期：——

  A series of novel dendritic iron(II) porphyrins with an axial imidazole ligand attached to the central porphyrin core was synthesised and fully characterised. The vacancy of the second axial coordination site was demonstrated by their ability to coordinate the diatomic gas molecules CO, O2 and NO. The formation of NO complexes by dendritic iron(II) porphyrins was observed for the first time.

  合成了一系列新型树枝状铁（II）卟啉，其中心卟啉核心连接有轴向咪唑配体，并进行了充分表征。第二个轴向配位位点的空缺通过其配位双原子气体分子 CO、O2 和 NO 的能力得到证明。首次观察到树枝状铁(II)卟啉形成NO复合物。
• Dendritic Iron Porphyrins with a Tethered Axial Ligand as New Model Compounds for Heme Monooxygenases
  作者：Philipp Weyermann、François Diederich

  DOI：10.1002/1522-2675(200202)85:2<599::aid-hlca599>3.0.co;2-v

  日期：2002.2
• Ferrocene Encapsulated within Symmetric Dendrimers:  A Deeper Understanding of Dendritic Effects on Redox Potential
  作者：Diane L. Stone、David K. Smith、P. Terry McGrail

  DOI：10.1021/ja0117478

  日期：2002.2.1

  Ferrocene has been encapsulated within a symmetric ether-amide dendritic shell and its redox potential monitored in a variety of solvents. The dendritic effect generated by the branched shell is different in different solvents. In less polar, non hydrogen bond donor solvents, attachment of the branched shell to ferrocene increases its E-1/2, indicating that oxidation to ferrocenium (charge buildup) becomes thermodynamically hindered by the dendrimer, a result explained by the dendrimer providing a less polar medium than that of the surrounding electrolyte solution. The effect of electrolyte concentration on redox potential was also investigated, and it was shown that the concentration of "innocent" electrolyte has a significant effect on the redox potential by increasing the overall polarity of the surrounding medium. Dendritic destabilization of charge buildup is in agreement with the majority of reported dendritic effects. A notable exception to this is provided by the asymmetric ferrocene dendrimers previously reported by Kaifer and co-workers, in which the branching facilitated oxidation, and it is proposed that in this case the dendritic effect is generated by a different mechanism. Interestingly, in methanol, the new symmetric ferrocene dendrimer exhibited almost no dendritic effect, a result explained by the ability of methanol to interact extensively with the branched shell, generating a more open superstructure. By comparison of all the new data with other reports, this study provides a key insight into the structure-activity relationships which control redox processes in dendrimers and also an insight into the electrochemical process itself.
• Catalytic Dendrophanes as Enzyme Mimics: Synthesis, Binding Properties, Micropolarity Effect, and Catalytic Activity of Dendritic Thiazolio-cyclophanes
  作者：Tilo Habicher、François Diederich、Volker Gramlich

  DOI：10.1002/(sici)1522-2675(19990707)82:7<1066::aid-hlca1066>3.0.co;2-o

  日期：1999.7.7

  Catalytic dendrophanes 9 and 10 were prepared as functional mimics of the thiamine-diphosphate-dependent enzyme pyruvate oxidase, and studied as catalysts in the oxidation of naphthalene-2-carbaldehyde (4) to methyl naphthalene-2-carboxylate (8) (Scheme 1). They are composed of a thiazolio-cyclophane initiator core with four generation-2 (G-2) poly(etheramide) dendrons attached. The two dendrophanes were synthesized by a convergent growth strategy by coupling dendrons 11 and 12, respectively (Scheme 2), with (chloromethyl)-cyclophane 42 (Scheme 5) and subsequent conversion with 4-methylthiaaole (Scheme 7). The X-ray crystal structures of cyclophane precursors 30 (Scheme 3), 37 and 38 (Scheme 5) on the way to dendrophanes were determined (Fig. I). The crystal-structure analysis of the benzene clathrate of 37 revealed the formation of channel-like stacks by the cyclophane which incorporate its morpholinomethyl side chain and the enclathrated benzene molecule (Fig. 2). The interactions of the enclathrated benzene molecule with the phenyl rings of the two adjacent cyclophane molecules in the stack closely resemble those between neighboring benzene molecules in crystalline benzene (Fig. 3). The characterization by MALDI-TOF-MS (Fig. 4) and H-1- and C-13-NMR spectroscopy (Fig. 5) proved the monodispersity of the G-2 dendrophanes 9 and 10 with molecular weights up to 11500 Da (Eor 10). H-1-NMR and fluorescence binding titrations in H2O and aqueous MeOH showed that 9 and 10 form stable 1:1 complexes with naphthalene-2-carbaldehyde (4) and 6-(p-toluidino)naphthalene-2-sulfonate (48, TNS) (Tables 1 and 2). The evaluation of the fluorescence-emission maxima of bound TNS revealed that the dendritic branching creates a microenvironment of distinctly reduced polarity at the cyclophane core by limiting its exposure to bulk solvent. Initial rate studies for the oxidation of naphthalene-2-carbaldehyde to methyl naphthalene-2-carboxylate in basic aqueous MeOH in the presence of flavin derivative 6 revealed only a weak catalytic activity of dendrophanes 9 and 10 (Table 3), despite the favorable micropolarity at the cyclophane active site. The low catalytic activity in the interior of the macromolecules was explained by steric hindrance of reaction transition states by the dendritic branches.
• Dendritic Iron Porphyrins with Tethered Axial Ligands: New Model Compounds for Cytochromes
  作者：Philipp Weyermann、François Diederich、Jean-Paul Gisselbrecht、Corinne Boudon、Maurice Gross

  DOI：10.1002/1522-2675(200202)85:2<571::aid-hlca571>3.0.co;2-y

  日期：2002.2

  porphyrins of generation zero ([1⋅FeIII]Cl), one ([2⋅FeIII]Cl), and two ([3⋅FeIII]Cl) (Fig. 1) were prepared as models of cytochromes (Schemes 1 and 2). They feature controlled axial ligation at the iron center by two imidazoles tethered to the porphyrin core. Similar to the core compound [4⋅FeIII]Cl, they are six-coordinate low-spin complexes as demonstrated by UV/VIS (Figs. 3 and 4) and EPR spectroscopy

  零代（[1⋅FeIII]Cl）、一个（[2⋅FeIII]Cl）和两个（[3⋅FeIII]Cl）（图1）的新型树枝状铁卟啉被制备为细胞色素模型（方案1 和 2）。它们的特点是通过拴在卟啉核心上的两个咪唑在铁中心控制轴向结扎。与核心化合物 [4·FeIII]Cl 类似，它们是六配位低自旋配合物，如 UV/VIS（图 3 和 4）和 EPR 光谱以及 Evans 对磁矩的测量所证明的 -舍福得法。还原成相应的铁 (II) 配合物后，配位环境不会改变。通过尺寸排阻色谱法纯化树枝状铁卟啉，并通过基质辅助激光解吸电离质谱法（MALDI-TOF-MS；图 5 和图 6）显示没有结构缺陷。凭借其三甘醇单甲醚表面基团，这三种树枝状模拟物可溶于极性差异很大的溶剂中。电化学研究（图 7 和图 8）和光学氧化还原滴定法（图 9）表明，在 CH2Cl2、MeCN 和 H2O 中 FeIII/FeII 对的电位强烈地移动到更正的值（高达