5-(4-amino-2-thiabutyl)-5-methyl-3,7-dithianonane-1,9-diamine | 81505-76-2

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: 5-(4-amino-2-thiabutyl)-5-methyl-3,7-dithianonane-1,9-diamine
• 英文别名: 4,4′,4″-ethylidynetris(3-thiabutan-1-amine)；4,4',4"-ethylidynetris(3-thiabutan-1-amine)；4,4',4''-ethylidynetris-(3-thiabutane-1-amine)；tris[2-(2-aminoethyl)thio]ethane；4,4',4''-Ethylidynetris(3-thiabutan-1-amine)；2-[3-(2-aminoethylsulfanyl)-2-(2-aminoethylsulfanylmethyl)-2-methylpropyl]sulfanylethanamine
• CAS: 81505-76-2
• 化学式: C₁₁H₂₇N₃S₃
• 分子量: 297.553
• InChiKey: RSVXECDMHJZJFB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0
• 重原子数：
  17
• 可旋转键数：
  12
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  154
• 氢给体数：
  3
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  5-(4-amino-2-thiabutyl)-5-methyl-3,7-dithianonane-1,9-diamine 在 sodium tetrahydroborate 作用下， 以 甲醇 、 乙醇 为溶剂， 反应 48.0h， 生成 2-[2-methyl-3-[2-[[6-(5-methylpyridin-2-yl)pyridin-3-yl]methylamino]ethylsulfanyl]-2-[2-[[6-(5-methylpyridin-2-yl)pyridin-3-yl]methylamino]ethylsulfanylmethyl]propyl]sulfanyl-N-[[6-(5-methylpyridin-2-yl)pyridin-3-yl]methyl]ethanamine
  参考文献：
  名称：

  带有三(联吡啶)铁(II)封端基团的笼配体的合成、表征和络合研究

  摘要：

  5-(4-amino-2-thiabutyl)-5-methyl-3,7-dithianonane-1,9-diamine (N3S3) 和 5-methyl-2,2-bipyridine-5-carbaldehyde 之间的反应和随后的还原生成的亚胺与硼氢化钠产生潜在的双位配体 (L)。用一当量的铁 (II) 盐处理 L 产生单质子化络合物 [Fe(HL)]3+，以六氟磷酸盐形式分离。在紫外/可见光谱中三（联吡啶）铁（II）发色团的特征带的存在表明铁（II）原子由三个联吡啶（bipy）基团八面体配位。[Fe(bipy)3] 部分包围了由双位配体的 N3S3 部分组成的空腔。配合物 [Fe(HL)]3+ 的单核和单体性质也已通过精确质量分析确定。与络合物 [Fe(bipy)3]2+ 相比，[Fe(HL)]3+ 对碱的稳定性降低。在水溶液中 [Fe(HL)]3+ 表现出不可逆的电化学行为，氧化波约为。60

  DOI：

  10.1071/ch02144
• 作为产物：
  描述：

  1,1,1-三(羟甲基)乙烷 在 sodium 、 三溴化磷 作用下， 以 乙醇 为溶剂， 反应 61.0h， 生成 5-(4-amino-2-thiabutyl)-5-methyl-3,7-dithianonane-1,9-diamine
  参考文献：
  名称：

  钴笼复合物作为蛋白质电子转移的介质

  摘要：

  摘要已选择具有N 3 S 3混合供体组但在单个顶部取代基上有所不同的钴（III）/（II）大双环'sarcophagine'（sar）笼状配合物，其氧化还原电位范围为+150至-150 mV与正常氢电极相比，因此在蛋白质光谱电化学和氧化还原电位测定中充当氧化还原缓冲液。钴（III）笼络合物均基于相同的母体结构[Co（X MeN 3 S 3 sar）] 3+，其中可变的顶部取代基X为–NO 2，–Cl，–OH，–NH 2，或–NMe + 3 ，甲基位于相反的顶端位置。报告了该系列中选定成员的X射线晶体结构。顶端取代基X的变化使Co III / II氧化还原电势可以通过官能团的感应作用在200 mV以上的范围内调节。氧化还原电势的pH依赖性使得可以确定某些官能团的p K a值。该配合物已成功地用作电子转移介质，用于各种血红素蛋白的光谱电化学研究。 图形概要

  DOI：

  10.1007/s00775-016-1427-y

文献信息

• The Synthesis and Properties of Cobalt Cage Complexes With N3S3 Donor Sets
  作者：PA Lay、J Lydon、AWH Mau、P Osvath、AM Sargeson、WHF Sasse

  DOI：10.1071/ch9930641

  日期：——

  An understanding of how variations in the cage ligands modify the redox behaviour of cobalt(II)/(III) couples has led to rational syntheses of a series N3S3 donor cobalt cage complexes that have redox potentials and electron self-exchange rates appropriate for their use as electron carriers in systems devised for the photoreduction of water. Diazotization of [Co(NH3-capten)]Cl4 (NH3-capten = 8-ammonio-1-methyl-3,13,16-trithia-6,10,19-triazabicyclo[6.6.6] icosane ) in nitric acid resulted in a mixture of five complexes: [Co(NO2-capten)]3+, [Co( Cl-capten )]3+ and [Co(HO- capten )]3+ (8-nitro-, 8-chloro- and 8-hydroxy-1-methyl-3,13,16-trithia-6,10,19-triazabicyclo[6.6.6] icosanecobalt (III) respectively), in which the cage framework remained intact, together with two complexes with a contracted cap, [Co(ClCH2-abcapten)]3+ and [Co(HOCH2-abcapten)]3+, (8-chloromethyl- and 8-hydroxymethyl-1-methyl-3,13,16-trithia-6,10,19-triazabicyclo[6.6.5] nonadecanecobalt (III), respectively). Reductive elimination occurred with [Co( Cl-capten )]3+ in the presence of Zn or Ni/Al alloy to give the parent cage complex, [Co( capten )]3+ (1-methyl-3,13,16-trithia-6,10,19-triazabicyclo[6.6.6] icosanecobalt (III)). When [Co(ten)]3+(4,4′,4″-ethylidynetris(3-thiabutan-1-amine)cobalt(III)) and an aqeuous solution of diethyl malonate and formaldehyde were reacted under basic conditions, the amide cage complex, [Co( EtOOC-oxocapten-H )]2+, (8-ethoxycarbonyl-1-methyl-3,13,16-trithia-6,10,19-triazabicyclo [6.6.6]icosan-7-onato(1-)cobalt(III)) was obtained. Hydrolysis of the ester group in base yielded the carboxylate derivative [Co(OOC- oxocapten - H)]+(8-carboxylate-1-methyl-3,13,16-trithia-6,10,19-triazabicyclo[6.6.6]icosan-7-onato(1-)cobalt(III)). The complexes were characterized by microanalyses, 1H and 13C n.m.r. spectroscopy, and electrochemistry. The values of the cobalt(III)/(II) redox potentials change with the nature of the apical substituents in a similar manner to that observed for the analogous hexaamine cage complexes, but they are all more positive, and the cobalt(II) complexes are low spin. The N3S3 donor set stabilizes the lower oxidation state and the low-spin electronic configuration. All of these cage complexes are effective at quenching the lowest lying triplet excited state of the [ Ru ( bpy )3]2+ complex, with rate constants typically c. 109 dm3 mol-1s-1. [Co( EtOOC-oxocapten-H )]2+ quenches [ Ru*( bpy )3]2+ very efficiently and has a suitable redox potential for hydrogen production, but it is only moderately efficient as an electron-transfer agent in the photoreduction of water. It is apparent that the high molar absorption coefficients of these cage complexes in the visible region, the too positive redox potentials and competing energy transfer and/or back electron-transfer inhibit their ability to be used as effective electron-transfer agents in these reactions at pH c. 5. However, the molecules are inherently interesting and stable redox reagents which undergo rapid one-electron reactions.

  通过了解笼配体的变化如何改变钴（II）/（III）偶联物的氧化还原行为，我们合理地合成了一系列 N3S3 给体钴笼配合物，这些配合物具有适当的氧化还原电位和电子自交换率，可在设计用于水的光还原的系统中用作电子载体。Co(NH3-capten)]Cl4（NH3-capten = 8-氨-1-甲基-3,13,16-三硫杂-6,10,19-三氮杂双环[6.6.6] icosane ）在硝酸中生成了五种络合物的混合物：[Co(NO2-capten)]3+、[Co( Cl-capten )]3+ 和 [Co(HO- capten )]3+ （8-硝基、8-氯基和 8-羟基-1-甲基-3,13,16-三硫杂-6,10,19-三氮杂双环[6.6.6]二十三烷基钴（III），其中笼形框架保持不变；还有两个带有收缩帽的配合物，即[Co(ClCH2-abcapten)]3+ 和[Co(HOCH2-abcapten)]3+（分别为 8-氯甲基和 8-羟甲基-1-甲基-3,13,16-三硫杂-6,10,19-三氮杂双环[6.6.5]十一烷基钴（III））。在 Zn 或 Ni/Al 合金存在下，[Co( Cl-capten )]3+ 发生还原消除反应，生成母笼络合物 [Co( capten )]3+ （1-甲基-3,13,16-三硫杂-6,10,19-三氮杂双环[6.6.6] 十氰基钴（III））。当[Co(10)]3+（4,4′,4″-乙叉三(3-噻烷-1-胺)钴(III)）与丙二酸二乙酯和甲醛的水溶液在碱性条件下反应时，酰胺笼配合物[Co( EtOOC-oxocapten-H )]2+ （8-乙氧羰基-1-甲基-3,13,16-三硫杂-6,10,19-三氮杂双环[6.6.6]icosan-7-onato(1-)cobalt(III) ）。酯基在碱中水解得到羧酸盐衍生物[Co(OOC- oxocapten - H)]+（8-羧酸盐-1-甲基-3,13,16-三硫杂-6,10,19-三氮杂双环[6.6.6]icosan-7-onato(1-)钴(III)）。这些配合物通过显微分析、1H 和 13C n.m.r. 光谱以及电化学进行表征。钴（III）/（II）氧化还原电位的值随顶端取代基性质的变化而变化，其变化方式与在类似的六胺笼络合物中观察到的相似，但它们都更正，而且钴（II）络合物是低自旋的。N3S3 给体组能稳定较低的氧化态和低自旋电子构型。所有这些笼状络合物都能有效淬灭[ Ru ( bpy )3]2+ 复合物的最低三重激发态，其速率常数通常约为 109 dm3 mol-1s-1。[Co( EtOOC-oxocapten-H )]2+ 能非常有效地淬灭[Ru*( bpy )3]2+，并具有适合制氢的氧化还原电位，但在水的光生还原过程中，它作为电子转移剂的效率很低。显然，这些笼状复合物在可见光区域的摩尔吸收系数较高、氧化还原电位过正以及存在竞争性能量转移和/或反向电子转移，这些因素都抑制了它们在 pH 值为 5 左右时作为有效电子转移剂用于这些反应的能力。不过，这些分子本身是有趣而稳定的氧化还原试剂，会发生快速的单电子反应。
• Lay, Peter A.; Lydon, John; Mau, Albert W.-H., Australian Journal of Chemistry, 1993, vol. 46, p. 641 - 662
  作者：Lay, Peter A.、Lydon, John、Mau, Albert W.-H.、Osvath, Peter、Sargeson, Alan M.、Sasse, Wolfgang H. F.

  DOI：——

  日期：——
• Donlevy, Therese M.; Gahan, Lawrence R.; Hambley, Trevor W., Australian Journal of Chemistry, 1993, vol. 46, # 11, p. 1799 - 1810
  作者：Donlevy, Therese M.、Gahan, Lawrence R.、Hambley, Trevor W.、McMahon, Katie L.、Stranger, Robert

  DOI：——

  日期：——
• A hexadentate nickel(II) complex with a tripodal ligand bearing S3N3 donors: Synthesis, spectroscopic and X-ray crystal structural investigation
  作者：Subrata Mandal、Parimal K. Bharadwaj、Zhong-Yuan Zhou、Thomas C.W. Mak

  DOI：10.1016/0277-5387(94)00313-4

  日期：1995.4

  A tripodal ligand, tris[2-(2-aminoethyl) thio]ethane (L(1)), bearing three thioether sulphurs and three primary amino nitrogens has been synthesized in high yield. Reaction with nickel(II) perchlorate hexahydrate yielded the complex [Ni(L(1))](ClO4)(2), which has been characterized by X-ray crystallography. The structure consists of two independent hexacoordinate cage cations and four independent perchlorate anions. The Ni-II ion is bound equatorially to two nitrogen and two sulphur atoms, while the other two donor atoms occupy the axial positions. Both the independent cage cations are disordered, with thioether sulphurs occupying two alternative sets of ligand sites. One of the four perchlorate anions is also disordered. IR, conductivity, RT magnetic susceptibility and electronic absorption spectral data are consistent with the solid state structure. The corresponding aromatic analogue, tris [2-(2-aminophenyl)thio]ethane (L(2)), forms the complex [Ni(L(2))](ClO4)(2), which has been characterized spectroscopically.
• Gahan, Lawrence R.; Hambley, Trevor W.; Sargeson, Alan M., Inorganic Chemistry, 1982, vol. 21, # 7, p. 2699 - 2706
  作者：Gahan, Lawrence R.、Hambley, Trevor W.、Sargeson, Alan M.、Snow, Michael R.

  DOI：——

  日期：——