bis<2,6-di(pivaloylamino)phenyl> disulfide | 164853-84-3

• 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-di(pivaloylamino)phenyl> disulfide
• 英文别名: bis(2,6-bis(pivaloylamino)phenyl) disulfide；N-[2-[[2,6-bis(2,2-dimethylpropanoylamino)phenyl]disulfanyl]-3-(2,2-dimethylpropanoylamino)phenyl]-2,2-dimethylpropanamide
• CAS: 164853-84-3
• 化学式: C₃₂H₄₆N₄O₄S₂
• 分子量: 614.874
• InChiKey: MYPGQZVKTJZZGD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.3
• 重原子数：
  42
• 可旋转键数：
  11
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  167
• 氢给体数：
  4
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (Et4N)2(Fe4S4(SPh)4) 、 bis<2,6-di(pivaloylamino)phenyl> disulfide 以 乙腈 为溶剂， 以40%的产率得到(NEt4)2[Fe4S4(S-2,6-(t-BuCONH)2C6H3)4]
  参考文献：
  名称：

  Structure and Properties of [Fe₄S₄{2,6-bis(acylamino)benzenethiolato-S}₄]^2- and [Fe₂S₂{2,6-bis(acylamino)benzenethiolato-S}₄]^2-:  Protection of the Fe−S Bond by Double NH···S Hydrogen Bonds

  摘要：

  Iron-sulfur clusters containing a singly or doubly NH...S hydrogen-bonded arenethiolate ligand, [Fe4S4(S-2-RCONHC(6)H(4))(4)](2-) (R = CH3, t-Bu, CF3), [Fe4S4{S-2,6-(RCONH)(2)C6H3}(4)](2-), [Fe2S2(S-2-RCONHC(6)H(4))(4)](2-) (R = CH3, t-Bu, CF3), and [Fe2S2{S-2,6-(RCONH)(2)C6H3}(4)](2-), were synthesized as models of bacterial [4Fe-4S] and plant-type [2Fe-2S] fenedoxins. The X-ray structures and IR spectra of (PPh(4))(2)[Fe4S4{S-2,6-(CH3-CONH)(2)C6H3}(4)]. 2CH(3)CN and (NEt(4))(2)[Fe2S2{S-2,6-(t-BuCONH)(2)C6H3}(4)] indicate that the two amide NH groups at the o,o'-positions are directed to the thiolate sulfur atom and form double NH...S hydrogen bonds. The NH...S hydrogen bond contributes to the positive shift of the redox potential of not only (Fe4S4)(+)/(Fe4S4)(2+) but also (Fe4S4)(2+)/(Fe4S4)(3+) in the [4Fe-4S] clusters as well as (Fe2S2)(2+)/(Fe2S2)(3+) in the [2Fe-2S] clusters. The doubly NH...S hydrogen-bonded thiolate ligand effectively prevents the ligand exchange reaction by benzenethiol because the two amide NH groups stabilize the thiolate by protection from dissociation.

  DOI：

  10.1021/ic9604324
• 作为产物：
  描述：

  bis(2,6-diaminophenyl) disulfide 、 三甲基乙酰氯 在 三乙胺 作用下， 以69%的产率得到bis<2,6-di(pivaloylamino)phenyl> disulfide
  参考文献：
  名称：

  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

  摘要：

  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.

  DOI：

  10.1021/jo00120a037

文献信息

• 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
• Effect of the NH---S Hydrogen Bond on the Nature of Hg−S Bonding in Bis[2-(acylamino)benzenethiolato]mercury(II) and Bis[2,6-bis(acylamino)benzenethiolato]mercury(II) Complexes
  作者：Norikazu Ueyama、Kaku Taniuchi、Taka-aki Okamura、Akira Nakamura、Hironobu Maeda、Shuichi Emura

  DOI：10.1021/ic950472s

  日期：1996.1.1

  2-(Acylamino)benzenethiolate complexes of Hg(II) having an intramolecular NH-S hydrogen bond, Hg[2-(pivaloylamino)benzenethiolato](2) and Hg[2,6-bis(pivaloylamino)benzenethiolato](2), were synthesized and the crystal structures were determined. The crystal structure of Hg[2-(pivaloylamino)benzenethiolato](2) . 1/2H(2)O shows the presence of two distinct conformers with different C-S-(Hg)-S-C torsion angles (81.7 and 176.6 degrees). The crystal structure of Hg[2,6-bis(pivaloylamino)benzenethiolato](2) indicates the presence of ordinary Hg-S bonds (2.335(2) and 2.342(2) Angstrom) and a straight linear coordination (S-Hg-S = 174.7(1)degrees) with a weak interaction of one of the amide CO groups toward HE(II). A weak NH-S hydrogen bond in both complexes is detected from the IR spectra in the solid state. The Hg-199 NMR spectra show the high-field shift with a decrease in the S --> Hg(II) ligand-to-metal charge transfer by the NH-S hydrogen bonding. The high-field shift by the double NH-S hydrogen bond is far greater than that by the p-substituent effect of the electron-withdrawing group (OMe, H, NHCOCH3, Cl, NO2) on the benzenethiolate ring.
• Structure and Properties of [Fe₄S₄{2,6-bis(acylamino)benzenethiolato-<i>S</i>}₄]²^- and [Fe₂S₂{2,6-bis(acylamino)benzenethiolato-<i>S</i>}₄]²^-:  Protection of the Fe−S Bond by Double NH···S Hydrogen Bonds
  作者：Norikazu Ueyama、Yusuke Yamada、Taka-aki Okamura、Shuuji Kimura、Akira Nakamura

  DOI：10.1021/ic9604324

  日期：1996.1.1

  Iron-sulfur clusters containing a singly or doubly NH...S hydrogen-bonded arenethiolate ligand, [Fe4S4(S-2-RCONHC(6)H(4))(4)](2-) (R = CH3, t-Bu, CF3), [Fe4S4S-2,6-(RCONH)(2)C6H3}(4)](2-), [Fe2S2(S-2-RCONHC(6)H(4))(4)](2-) (R = CH3, t-Bu, CF3), and [Fe2S2S-2,6-(RCONH)(2)C6H3}(4)](2-), were synthesized as models of bacterial [4Fe-4S] and plant-type [2Fe-2S] fenedoxins. The X-ray structures and IR spectra of (PPh(4))(2)[Fe4S4S-2,6-(CH3-CONH)(2)C6H3}(4)]. 2CH(3)CN and (NEt(4))(2)[Fe2S2S-2,6-(t-BuCONH)(2)C6H3}(4)] indicate that the two amide NH groups at the o,o'-positions are directed to the thiolate sulfur atom and form double NH...S hydrogen bonds. The NH...S hydrogen bond contributes to the positive shift of the redox potential of not only (Fe4S4)(+)/(Fe4S4)(2+) but also (Fe4S4)(2+)/(Fe4S4)(3+) in the [4Fe-4S] clusters as well as (Fe2S2)(2+)/(Fe2S2)(3+) in the [2Fe-2S] clusters. The doubly NH...S hydrogen-bonded thiolate ligand effectively prevents the ligand exchange reaction by benzenethiol because the two amide NH groups stabilize the thiolate by protection from dissociation.
• 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.