N-(2-mercaptopropyl)-N,N-bis(2-pyridylmethyl)amine

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: N-(2-mercaptopropyl)-N,N-bis(2-pyridylmethyl)amine
• 英文别名: 1-(bis(pyridin-2-ylmethyl)amino)propane-2-thiol
• 化学式: C₁₅H₁₉N₃S
• 分子量: 273.402
• InChiKey: LNUOEMJGDSSNAF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  19.0
• 可旋转键数：
  6.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  29.02
• 氢给体数：
  1.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  N-(2-mercaptopropyl)-N,N-bis(2-pyridylmethyl)amine 在 碘 作用下， 以 甲醇 、 乙腈 为溶剂， 反应 1.0h， 生成
  参考文献：
  名称：

  具有生物相关性的CuIIμ-硫氰酸盐复合物的质子化：配体解离或质子化的CuI二硫键物种的形成？

  摘要：

  一个Cu的质子诱导的电子转移反应II μ-硫醇盐配合物与Cu我含物种已经研究，实验和计算。在Cu II μ-硫醇盐配合物[铜II 2（大号我小号）2 ] 2+分离为具有新的含吡啶基配体大号我SSL我，可形成既铜II硫醇盐和Cu我二硫化物的复合物，这取决于溶剂。Cu II和Cu I配合物在添加质子时显示出反应性。多价四核络合物[Cu I 2 Cu II 2（LS）2（CH 3 CN）6 ] 4+在向含μ-硫醇盐络合物[Cu II 2（LS）2的溶液中添加两当量的强酸后结晶。] 2+，并在溶液中进一步分析。这项研究表明，将质子添加到Cu II硫醇盐化合物后，配体会从铜中心解离，这与先前报道的将氧化还原异构化为Cu I的报道相反。在吡啶基部分质子化的二硫化物。该质子化的Cu的计算研究II μ-硫醇盐和Cu我二硫化物物质与LSSL表明已经在加入两个当量的质子的，配位体离解形成的[铜我（CH 3 CN）4

  DOI：

  10.1002/chem.201403918
• 作为产物：
  描述：

  环丙硫醇 、 二甲基吡啶胺 以 乙腈 为溶剂， 反应 15.0h， 以80%的产率得到N-(2-mercaptopropyl)-N,N-bis(2-pyridylmethyl)amine
  参考文献：
  名称：

  Cu^I Thiolate Reactivity with Dioxygen: The Formation of Cu^II Sulfinate and Cu^II Sulfonate Species via a Cu^II Thiolate Intermediate

  摘要：

  Cu-I(Py2NS) (1) is formed by addition of Cu-I to a solution of the pyridyl-thiol ligand N-(2-mercaptopropyl)-N,N-bis(2-pyridylmethyl)amine (Py2NSH). Oxidation of complex 1 by air leads to the formation of Cu-II sulfinate and Cu-II sulfonate complexes, providing a model for the oxidative degeneration of copper-sulfur enzymes. Crystal structures were obtained for two Cu-II sulfinate complexes, [Cu-2(II)(Py2NSO2)(2)](BF4)(2)center dot 2(CH3)(2)CO (4a) and [Cu-2(II)(Py2NSO2)(2)(OTf)(2)] (4b), which were further characterized by UV-vis and EPR spectroscopy and cyclic voltammetry. Furthermore, two Cu-II sulfonate complexes with the proposed formulas Cu-2(II)(Py2NSO3)(2)(BF4)(2) (5a) and Cu-2(II)(Py2NSO3)(2)(OTf)(2) (5b) have been isolated and characterized. Monitoring the oxidation of 1 by UV-vis indicates that the oxidation proceeds via a dinuclear Cu-II mu-thiolate complex (3); as an intermediate an octanuclear mixed-valent (Cu4Cu4II)-Cu-I cluster with formula [(Cu4Cu4II)-Cu-I(Py2NS)(4)(mu-OH)(2)(CH3CN)(6)](ClO4)(6)center dot 2CH(3)CN (2) was isolated and characterized by X-ray single crystal structure determination.

  DOI：

  10.1021/ic402001t

文献信息

• Catalytic catechol oxidation by copper complexes: development of a structure–activity relationship
  作者：Erica C. M. Ording-Wenker、Maxime A. Siegler、Martin Lutz、Elisabeth Bouwman

  DOI：10.1039/c5dt01041a

  日期：——

  High activity for the catalytic oxidation of 3,5-di-tert-butylcatechol was achieved with complexes of ligands that stabilize the biomimetic Cu^II μ-thiolate complex, hinting at a similarity with the required Cu-oxo intermediates.

  使用能稳定生物拟态Cu^IIμ-硫醇盐络合物的配体实现了对3,5-二叔丁基邻苯二酚的催化氧化的高活性，这暗示了与所需的Cu-过氧中间体之间的相似性。
• N3S-ligated Copper(II) Complex Catalyzed Selective Oxidation of Benzylic Alcohols to Aldehydes under Mild Reaction Conditions
  作者：Sivanesan Dharmalingam、Eunhae Koo、Sungho Yoon、Gyoosoon Park

  DOI：10.5012/bkcs.2014.35.3.715

  日期：2014.3.20

  A Cu(II) complex with an three nitrogens and one sulfur coordination environment was synthesized and characterized. Its redox potential was observed at 0.483 V vs. NHE, very similar to that of a Cu-containing fungal enzyme, galactose oxidase, which catalyzes the oxidation of alcohols to corresponding aldehydes with the concomitant reduction of molecular oxygen to water. The Cu(II) complex selectively

  合成并表征了具有三个氮和一个硫配位环境的 Cu(II) 配合物。在 0.483 V vs. NHE 下观察到其氧化还原电势，与含铜真菌酶半乳糖氧化酶的氧化还原电势非常相似，半乳糖氧化酶催化醇氧化为相应的醛，同时将分子氧还原为水。Cu(II) 配合物在温和的反应条件下使用 TEMPO/选择性地将苄醇氧化成相应的醛，而不会形成任何过氧化产物。此外，催化剂可以多次回收和重复用于进一步的氧化反应，从而最大限度地减少废物的产生。
• Protonation of a Biologically Relevant Cu^IIμ-Thiolate Complex: Ligand Dissociation or Formation of a Protonated Cu^IDisulfide Species?
  作者：Erica C. M. Ording-Wenker、Martijn van der Plas、Maxime A. Siegler、Célia Fonseca Guerra、Elisabeth Bouwman

  DOI：10.1002/chem.201403918

  日期：2014.12.15

  isomerization to a CuI disulfide species that is protonated at the pyridyl moieties. Computational studies of the protonated CuII μ‐thiolate and CuI disulfide species with LSSL show that already upon addition of two equivalents of protons, ligand dissociation forming [CuI(CH3CN)4]+ and protonated ligand is energetically favored over conversion to a protonated CuI disulfide complex.

  一个Cu的质子诱导的电子转移反应II μ-硫醇盐配合物与Cu我含物种已经研究，实验和计算。在Cu II μ-硫醇盐配合物[铜II 2（大号我小号）2 ] 2+分离为具有新的含吡啶基配体大号我SSL我，可形成既铜II硫醇盐和Cu我二硫化物的复合物，这取决于溶剂。Cu II和Cu I配合物在添加质子时显示出反应性。多价四核络合物[Cu I 2 Cu II 2（LS）2（CH 3 CN）6 ] 4+在向含μ-硫醇盐络合物[Cu II 2（LS）2的溶液中添加两当量的强酸后结晶。] 2+，并在溶液中进一步分析。这项研究表明，将质子添加到Cu II硫醇盐化合物后，配体会从铜中心解离，这与先前报道的将氧化还原异构化为Cu I的报道相反。在吡啶基部分质子化的二硫化物。该质子化的Cu的计算研究II μ-硫醇盐和Cu我二硫化物物质与LSSL表明已经在加入两个当量的质子的，配位体离解形成的[铜我（CH 3 CN）4
• Cu^I Thiolate Reactivity with Dioxygen: The Formation of Cu^II Sulfinate and Cu^II Sulfonate Species via a Cu^II Thiolate Intermediate
  作者：Erica C.M. Ording-Wenker、Maxime A. Siegler、Martin Lutz、Elisabeth Bouwman

  DOI：10.1021/ic402001t

  日期：2013.11.18

  Cu-I(Py2NS) (1) is formed by addition of Cu-I to a solution of the pyridyl-thiol ligand N-(2-mercaptopropyl)-N,N-bis(2-pyridylmethyl)amine (Py2NSH). Oxidation of complex 1 by air leads to the formation of Cu-II sulfinate and Cu-II sulfonate complexes, providing a model for the oxidative degeneration of copper-sulfur enzymes. Crystal structures were obtained for two Cu-II sulfinate complexes, [Cu-2(II)(Py2NSO2)(2)](BF4)(2)center dot 2(CH3)(2)CO (4a) and [Cu-2(II)(Py2NSO2)(2)(OTf)(2)] (4b), which were further characterized by UV-vis and EPR spectroscopy and cyclic voltammetry. Furthermore, two Cu-II sulfonate complexes with the proposed formulas Cu-2(II)(Py2NSO3)(2)(BF4)(2) (5a) and Cu-2(II)(Py2NSO3)(2)(OTf)(2) (5b) have been isolated and characterized. Monitoring the oxidation of 1 by UV-vis indicates that the oxidation proceeds via a dinuclear Cu-II mu-thiolate complex (3); as an intermediate an octanuclear mixed-valent (Cu4Cu4II)-Cu-I cluster with formula [(Cu4Cu4II)-Cu-I(Py2NS)(4)(mu-OH)(2)(CH3CN)(6)](ClO4)(6)center dot 2CH(3)CN (2) was isolated and characterized by X-ray single crystal structure determination.