bis(2,6-diaminophenyl) disulfide | 1753-93-1

• 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: bis(2,6-diaminophenyl) disulfide
• 英文别名: 2-[(2,6-Diaminophenyl)disulfanyl]benzene-1,3-diamine
• CAS: 1753-93-1
• 化学式: C₁₂H₁₄N₄S₂
• 分子量: 278.402
• InChiKey: MURJDVSXFFJMPY-UHFFFAOYSA-N

物化性质

• 熔点：
  181 °C
• 沸点：
  484.9±45.0 °C(Predicted)
• 密度：
  1.45±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  155
• 氢给体数：
  4
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  bis(2,6-diaminophenyl) disulfide 生成 7-碘-苯并[1,2,3]噻二唑
  参考文献：
  名称：

  183. 1,2,3-苯并噻二唑。第三部分 5-和7-氨基1,2,3-苯并噻二唑的亲电取代反应和一些取代的1,2,3-苯并噻二唑的制备

  摘要：

  DOI：

  10.1039/jr9650001023

文献信息

• Snapshot of Oxidation of Thiolate by Diiodine: Stabilization of Intermediate by NH···S Hydrogen Bonds
  作者：Taka-aki Okamura、Toshihisa Kaga、Satoshi Yamashita、Ryosuke Furuya、Kiyotaka Onitsuka

  DOI：10.1021/acs.joc.7b00160

  日期：2017.2.17

  reaction. In the case of thiolate Ar1S– containing very bulky acylamino groups forming NH···S hydrogen bonds, the crystal of the intermediate, [Ar1S–I–I]−, was obtained under usual conditions, and the structure was determined by X-ray diffraction analysis. The results show that the intramolecular NH···S hydrogen bonds stabilized the intermediate [Ar1S–I–I]−, consistent with theoretical calculations.

  普通硫醇盐（RS –）与二碘（I 2）反应，通过释放I –生成中间体亚硫基碘（RSI）。RSI易于通过歧化反应转化为二硫键（RSSR）。在硫醇盐的情况下的Ar 1小号-含有形成NH ...小号氢键，中间的晶体非常笨重酰氨基，[氩1 S-I-I] - ，被通常的条件下获得的，并且该结构是通过X射线衍射分析确定。结果表明，分子内NH···S氢键稳定了中间体[ Ar 1 S–I–I] -，与理论计算结果一致。
• Cooperative Redox Regulation of [4Fe-4S] Ferredoxin Model Arenethiolate Complexes by NH···S Hydrogen Bonds and an Aromatic C–H···S Interaction
  作者：Takafumi Ueno、Masahiro Inohara、Norikazu Ueyama、Akira Nakamura

  DOI：10.1246/bcsj.70.1077

  日期：1997.5

  A series of the model complexes containing ortho-substituted arenethiolato ligands, ((Et4N)2[Fe4S4(S-2-RCONHC6H4)4] R = Ph (1), 4-MeO–C6H4 (2), and 4-F–C6H4 (3)} and (Et4N)2[Fe4S4S-2,6-(RCONH)2C6H3}4] R = Ph (4), 4-MeO–C6H4 (5), and 4-F–C6H4 (6)}) was synthesized and characterized by 1H NMR, IR spectroscopy, and cyclic voltammetry. The solution structures of these complexes are discussed based on their 1H NMR T1 data and molecular-dynamics calculations. Complex 4 has a shorter distance (av. 4.3 Å) between the protons of the benzoyl group and the inorganic sulfur atom of the [4Fe-4S] cluster than the corresponding ones of 1 (av. 6.2 Å). These results indicate the C–H···S interaction between the protons of the benzoyl group and the sulfur atom of the [4Fe-4S] cluster. The [Fe4S4(SAr)4]2−/[Fe4S4(SAr)4]3−redox potential for 1 and 4 are −0.86 and −0.65 V, respectively. The difference between 1 and 4 is Δ0.21 V. This is larger than the value Δ0.11 V between [Fe4S4(S-2-t-BuCONHC6H4)4]2− (−0.91 V) and [Fe4S4S-2,6-(t-BuCONH)2C6H3}4]2− (−0.80 V), considered to be the difference between singly and doubly NH···S hydrogen-bonded complexes. The redox potentials for 1—6 follow the trend of the Hammett σm values, showing that the aromatic ring of the benzoyl group interacts with the [4Fe-4S] cluster directly. A cooperative effect between the C–H···S interaction and the NH···S hydrogen bond is thus found to regulate the redox potential of the model complexes.

  合成了一系列含有正交取代的壬硫醇配体的模型配合物（(Et4N)2[Fe4S4(S-2-RCONH )4] R = Ph (1)、4-MeO-C6H4 (2) 和 4-F- (3)} 和 (Et4N)2[Fe4S4S-2、6-(RCONH)2C6H3}4] R = Ph (4)、4-MeO- (5) 和 4-F- (6)}）的合成，并通过 1H NMR、红外光谱和循环伏安法对其进行了表征。根据它们的 1H NMR T1 数据和分子动力学计算，讨论了这些配合物的溶液结构。与 1 的相应距离（平均 6.2 Å）相比，配合物 4 的苯甲酰基质子与 [4Fe-4S] 簇的无机硫原子间的距离（平均 4.3 Å）更短。这些结果表明，苯甲酰基的质子与[4Fe-4S]簇的硫原子之间存在着 C-H-S 相互作用。1 和 4 的 [Fe4S4(SAr)4]2-/[Fe4S4(SAr)4]3- 氧化还原电位分别为 -0.86 V 和 -0.65 V。这比[Fe4S4(S-2-t-BuCONH )4]2-（-0.91 V）和[Fe4S4S-2,6-(t-BuCONH)2C6H3}4]2-（-0.80 V）之间的差值Δ0.11 V要大，后者被认为是单重和双重NH--·S氢键配合物之间的差值。1-6 的氧化还原电位与 Hammett σm 值的趋势一致，表明苯甲酰基的芳香环直接与 [4Fe-4S] 簇相互作用。因此发现 C-H-S 相互作用和 NH-S 氢键之间的合作效应调节着模型配合物的氧化还原电位。
• One Ligand Fits All: Formation and Stabilization of a Single‐Ligand Arenethiolato Cobalt(II) Complex via Metal‐π Coordination from a Bulky Acylamino Group
  作者：Yusuke Tomita、Taka‐aki Okamura、Kiyotaka Onitsuka

  DOI：10.1002/ejic.202200546

  日期：2022.12.27

  A single-ligand mononuclear cobalt(II) complex is presented, which has one highly bulky arenethiolato ligand containing acylamino groups. The complex was stabilized by S,N-chelate and strong π-coordination with a quasi-square-planar geometry resulting in a low-spin state. Interestingly, the π-coordination was reversible in response to the solvent accompanying the spin-state transition.

  提出了一种单配体单核钴 (II) 络合物，它具有一个含有酰氨基的大体积芳硫醇配体。该复合物通过 S、N-螯合物和强 π-配位稳定，具有准方形平面几何形状，从而导致低自旋状态。有趣的是，随着自旋态转变伴随着溶剂，π配位是可逆的。
• Syntheses and Structures of Arenethiolato Cobalt(II) Complexes Containing Acylamino Groups: Steric Effects of Bulky Ligands on Coordination and Geometry
  作者：Yusuke Tomita、Taka-aki Okamura、Yuki Umeda、Koichiro Nishimoto、Satoshi Yamashita、Kiyotaka Onitsuka

  DOI：10.1021/acs.inorgchem.3c00849

  日期：2023.6.5

  Bulky thiolato ligands have been developed for creating biomimetic model complexes of active sites in metalloenzymes. Herein, we report a series of di-ortho-substituted arenethiolato ligands containing bulky acylamino groups (RCONH; R = t-Bu–, (4-t-BuC6H4)3C–,3,5-(Me2CH)2C6H3}3C–, and 3,5-(Me3Si)2C6H3}3C−) that were developed for biomimetics. Bulky hydrophobic substituents generate a hydrophobic

  大体积的硫醇配体已被开发用于创建金属酶活性位点的仿生模型复合物。在此，我们报道了一系列含有大量酰基氨基的二邻位取代芳硫醇配体 (RCONH; R = t -Bu–, (4- t -BuC 6 H 4 ) 3 C–,3,5-(Me 2 CH) 2 C 6 H 3 } 3 C–和3,5-(Me 3 Si) 2 C 6 H 3 } 3C-) 是为仿生学开发的。庞大的疏水取代基通过 NHCO 键在配位硫原子周围产生疏水空间。这种空间环境诱导低配位单核硫醇 Co(II) 配合物的形成。疏水空间中定位良好的 NHCO 部分以不同的配位模式与钴中心的空位配位，即羰基 C=O 的 S,O-螯合物或酰氨基 CON 的 S,N-螯合物–。使用单晶 X 射线晶体学详细研究了复合物的固体（结晶）和溶液结构，1H NMR 和吸收光谱分析。NHCO 的自发去质子化通常在金属酶中观察到，但在人工系统中需要强碱，通过
• Crystal and Solution Structures of Novel Bulky Bis[2,6-bis(acylamino)phenyl] Disulfides. Absence of Covalent NH.cntdot..cntdot..cntdot.S Hydrogen Bond between Amide NH and Neighboring Disulfide in Bis[2,6-bis(pivaloylamino)phenyl] Disulfide
  作者：Norikazu Ueyama、Taka-aki Okamura、Yusuke Yamada、Akira Nakamura

  DOI：10.1021/jo00120a037

  日期：1995.7

  Novel bulky bis[2,6-di(acylamino)phenyl] disulfides, e.g. bis[2,6-di(pivaloylamino)phenyl] disulfide and bis[2,6-di(triphenylacetylamino)phenyl] disulfide, having two acylamino groups at the 2,6-positions of the benzene ring were synthesized and the crystal structures determined. The two bulky acylamino groups cover the disulfide group, and the two amide NH groups are directed toward the sulfur atom, but the IR NH bands observed in the solid state indicate the absence of covalent NH-S hydrogen bonds in bis[2, 6-di(pivaloylamino)phenyl] disulfide.