di-2-(N-cyclohexyl,N-(methylamino)methyl)phenyl diselenide | 141819-06-9

• 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: di-2-(N-cyclohexyl,N-(methylamino)methyl)phenyl diselenide
• 英文别名: 2,2'-selenobis(N-cyclohexyl-N-methylbenzylamine)；Benzenemethanamine, 2,2'-diselenobis[N-cyclohexyl-N-methyl-；N-[[2-[[2-[[cyclohexyl(methyl)amino]methyl]phenyl]diselanyl]phenyl]methyl]-N-methylcyclohexanamine
• CAS: 141819-06-9
• 化学式: C₂₈H₄₀N₂Se₂
• 分子量: 562.559
• InChiKey: SGMBZSDMDRMBSC-UHFFFAOYSA-N

物化性质

• 沸点：
  612.8±65.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.49
• 重原子数：
  32
• 可旋转键数：
  9
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  6.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  di-2-(N-cyclohexyl,N-(methylamino)methyl)phenyl diselenide 在 溴 作用下， 以 二氯甲烷 为溶剂， 以100%的产率得到2-<(N-cyclohexyl-N-methylamino)methyl>benzeneselenyl bromide
  参考文献：
  名称：

  Iwaoka, Michio; Tomoda, Shuji, Phosphorus, Sulfur and Silicon and the Related Elements, 1992, vol. 67, # 1-4, p. 125 - 130

  摘要：

  DOI：
• 作为产物：
  描述：

  methyl 2-selenocyanatobenzoate 在 吡啶 、 盐酸 、 lithium aluminium tetrahydride 、 氯化亚砜 、 air 、 potassium carbonate 作用下， 以 二氯甲烷 、 水 、 丙酮 为溶剂， 反应 54.0h， 生成 di-2-(N-cyclohexyl,N-(methylamino)methyl)phenyl diselenide
  参考文献：
  名称：

  Iwaoka, Michio; Tomoda, Shuji, Phosphorus, Sulfur and Silicon and the Related Elements, 1992, vol. 67, # 1-4, p. 125 - 130

  摘要：

  DOI：

文献信息

• Structural characteristics of areneselenenyl bromide and areneselenenyl chloride stabilized by hypervalent coordination with a halide anion in the solid state
  作者：Michio Iwaoka、Hiroto Komatsu、Shuji Tomoda

  DOI：10.1016/s0022-328x(00)00434-4

  日期：2000.10

  Solid-state molecular structures of 2-[(N-cyclohexyl-N-methylamino)methyl]benzeneselenenyl bromide (ArSeBr) and chloride (ArSeCl), stabilized by hypervalent coordination with a halide anion (Br− or Cl−, respectively), were determined by X-ray diffraction method. By comparing bond parameters of the observed hypervalent BrSe⋯Br fragment with those reported previously for other organoselenium compounds

  的2个固态分子结构- [（Ñ -环己Ñ甲氨基）甲基] benzeneselenenyl溴化物（ArSeBr）和氯化（ArSeCl），通过超价协调与卤化物阴离子（BR稳定-或Cl -分别通过X射线衍射法测定。通过将观察到的高价BrSe⋯Br片段的键参数与先前报道的具有类似T形硒片段的其他有机硒化合物的键参数进行比较，发现两个线性SeBr原子之间存在良好的双曲关系。固态距离，反映了溶液中苯硒基溴化物（PhSeBr）加成反应的途径的可能性。此外，通过比较固态的外推SeBr共价键长度（2.220Å）和PhSeBr（2.325）报道的值，强烈暗示了由于分子间弱堆积相互作用而导致的显着键缩短（〜0.1Å）。 Å）在气相中。从头计算分子在RHF / 6-31G（d，-1与包装结构无关。
• Nature of the Intramolecular Se···N Nonbonded Interaction of 2-Selenobenzylamine Derivatives. An Experimental Evaluation by ¹H, ⁷⁷Se, and ¹⁵N NMR Spectroscopy
  作者：Michio Iwaoka、Shuji Tomoda

  DOI：10.1021/ja953358h

  日期：1996.1.1

  H-1 NMR analysis of seven 2-selenobenzylamine derivatives (ArSeX, 1-7) has revealed the existence of attractive nonbonded interaction between the divalent selenium and an unsymmetric amino nitrogen, whose strength significantly depends on the relative electrophilic reactivity of the selenium moiety. In the intermediate cases (5, X=CN; 6, X=SPh), the dissociation energy of the Se ... N nonbonded interaction was evaluated as 12.4 and 10.8 kcal/mol, respectively, by variable-temperature H-1 NMR spectral simulations. The corresponding values were roughly estimated as >18.8 kcal/mol for the strong cases (2, X=Br; 3, X=Cl; 4, X=OAc) and <7.7 kcal/mol for the weak cases (1, X=SeAT; 7, X=Me). In order to elucidate physicochemical properties of the interactilon, N-15-labeled compounds were synthesized. Downfield shifts of N-15 NMR (Delta delta(N)) and increment of J(Se ... N) (coupling constant between Se-77 and N-15) were observed with increasing Se ... N interaction. In the case of strong Se ... N interaction, saturation of coupling constants was observed. These experimental observations as well as large NBO deletion energies (3-21G* and LANL1DZ) between the selenium and the nitrogen for model compounds (9-13) strongly suggested that the observed Se ... N interaction is mainly caused by the orbital interaction between the nitrogen lone pair (n(N)) and the antibonding orbital of the Se-X bond (sigma*(Se-X)).
• A Model Study on the Effect of an Amino Group on the Antioxidant Activity of Glutathione Peroxidase
  作者：Michio Iwaoka、Shuji Tomoda

  DOI：10.1021/ja00085a040

  日期：1994.3

  In order to investigate mechanistic roles of the amino nitrogens located at the active center of glutathione peroxidase (GPX), a selenium-containing antioxidant enzyme, kinetic analyses and characterization of the intermediates of the model reaction (H2O2 + 2PhSH - 2H2O + PhSSPh) catalyzed by di-2-(N-cyclohexyl,N-(methylamino)methyl)phenyl diselenide (1) have been performed. The rate equation in methanol at 25-degrees-C by changing the initial concentrations of H2O2 and catalyst 1 suggests that the model catalyst (1) behaves precisely like GPX in the reduction catalytic cycle. On the basis of the Se-77 NMR experiments in a 1:1 mixture of CD3OD and CDCl3 under rigorous nitrogen atmosphere, three intermediates, selenenyl sulfide 4, selenolate 5', and selenenic acid 6, are characterized. Three specific roles of proximate nitrogen atoms on the GPX-like activity are proposed. (1) Both theory (MO calculation) and experiments (Se-77 NMR) suggest that the proximate nitrogen base activates the selenol intermediate (5) into the corresponding selenolate anion (5', Se-77 NMR observed at delta 22 ppm), which should play a key role in accelerating the catalytic cycle. (2) The proximate nitrogen moiety stabilizes otherwise elusive selenenic acid intermediate (6), which is observable by Se-77 NMR (delta 1173 ppm). It is suggested by this direct observation of the selenenic acid intermediate that intramolecular Se-N interaction prevents its deterioration by further oxidation in the catalytic system. (3) Since the formation of an Se-N hypervalent bonding is demonstrated by low-temperature dynamic H-1 NMR experiment for the selenenyl sulfide intermediate (4), it is expected that the nucleophilic attack of benzenethiol (PhSH) should occur preferentially at the sulfur atom of 4, allowing effective production of the selenolate intermediate (5') in the catalytic cycle.