bis(1-methyl-1H-imidazol-2-ylthio)methane | 210532-91-5

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: bis(1-methyl-1H-imidazol-2-ylthio)methane
• 英文别名: bis((1-methylimidazol-3-yl)thio)methane；bis(1-methylthioimidazolyl)methane；CH2(S-tim)2；1-Methyl-2-[(1-methylimidazol-2-yl)sulfanylmethylsulfanyl]imidazole
• CAS: 210532-91-5
• 化学式: C₉H₁₂N₄S₂
• 分子量: 240.353
• InChiKey: YMXGMZZRZPRSKU-UHFFFAOYSA-N

物化性质

• 熔点：
  51-52 °C
• 沸点：
  445.0±55.0 °C(Predicted)
• 密度：
  1.34±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  86.2
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  bis(1-methyl-1H-imidazol-2-ylthio)methane 生成 bis(1-methyl-imidazole-2-thione)methane
  参考文献：
  名称：

  Unexpected New Chemistry of the Bis(thioimidazolyl)methanes

  摘要：

  [GRAPHICS]The synthesis of the linkage isomers of the bis(thioimidazolyl)methane family of compounds, namely CH2(N-tim)(2) (1) and CH2(S-tiM)(2) (2) (where tim = thio(methyl)imidazolyl) has been reinvestigated in order to optimize the yields, to complete the characterization of these known compounds, and also to ascertain the effect of varying heteroatom binding on their electrochemistry. During the course of these studies, the reactive intermediate CICH2(S-tiM) (3) was isolated and characterized. The chloromethyl derivative 3 readily decomposes on warming to give the ionic compound [CH2-(mu-C4H5N2S)(2)CH2](Cl)(2) (4), which was converted to the hexafluorophosphate salt (5) and then was characterized by single-crystal X-ray diffraction. It was also shown that CH2(S-tiM)(2) (2) could be converted at temperatures greater than 120 degrees C to CH2(N-tim)(2) (1) by a thermal isomerization that proceeds via the remaining possible linkage isomer CH2(S-tim)(N-tim). Electrochemical studies on 1-3 in acetonitrile reveals that each undergoes irreversible (one electron per ring) oxidations above 0.7 V versus Ag/AgCl, while the ionic compound 5 shows an irreversible reduction wave centered at -1.09 V.

  DOI：

  10.1021/jo051101o
• 作为产物：
  描述：

  二氯甲烷 、 甲巯咪唑 在 氢氧化钾 、 四丁基溴化铵 、 potassium carbonate 作用下， 以 水 为溶剂， 反应 24.0h， 以22%的产率得到2-((chloromethyl)thio)-1-methyl-1H-imidazole
  参考文献：
  名称：

  Unexpected New Chemistry of the Bis(thioimidazolyl)methanes

  摘要：

  [GRAPHICS]The synthesis of the linkage isomers of the bis(thioimidazolyl)methane family of compounds, namely CH2(N-tim)(2) (1) and CH2(S-tiM)(2) (2) (where tim = thio(methyl)imidazolyl) has been reinvestigated in order to optimize the yields, to complete the characterization of these known compounds, and also to ascertain the effect of varying heteroatom binding on their electrochemistry. During the course of these studies, the reactive intermediate CICH2(S-tiM) (3) was isolated and characterized. The chloromethyl derivative 3 readily decomposes on warming to give the ionic compound [CH2-(mu-C4H5N2S)(2)CH2](Cl)(2) (4), which was converted to the hexafluorophosphate salt (5) and then was characterized by single-crystal X-ray diffraction. It was also shown that CH2(S-tiM)(2) (2) could be converted at temperatures greater than 120 degrees C to CH2(N-tim)(2) (1) by a thermal isomerization that proceeds via the remaining possible linkage isomer CH2(S-tim)(N-tim). Electrochemical studies on 1-3 in acetonitrile reveals that each undergoes irreversible (one electron per ring) oxidations above 0.7 V versus Ag/AgCl, while the ionic compound 5 shows an irreversible reduction wave centered at -1.09 V.

  DOI：

  10.1021/jo051101o

文献信息

• Ligand-Promoted Solvent-Dependent Ionization and Conformational Equilibria of Re(CO)₃Br[CH₂(<i>S</i>-tim)₂] (tim = 1-methylthioimidazolyl). Crystal Structures of Re(CO)₃Br[CH₂(<i>S</i>-tim)₂] and {Re(CO)₃(CH₃CN)[CH₂(S-tim)₂]}(PF₆)
  作者：Rosalice M. Silva、Brendan J. Liddle、Sergey J. Lindeman、Mark D. Smith、James R. Gardinier

  DOI：10.1021/ic060765t

  日期：2006.8.1

  ionization to form Re(CO)3(CH3CN)[CH2(S-tim)2]+}(Br-) in acetonitrile. Ionization does not occur in solvents such as CH2Cl2 or acetone that are less polar and Lewis basic (less coordinating). The equilibrium constant at 293 K for the ionization of 1 in CH3CN is 4.3 x 10(-3). The eight-member chelate rings in each 1 and 2 were found to be conformationally flexible in all solvents, and boat-chair conformers

  化合物Re（CO）3Br [ （S-tim）2]（1）和Re（CO）3（CH3CN）[ （S-tim）2]}（PF6）（2），其中tim是1高产率地制备了-甲基硫代咪唑基，并以固态和溶液形式对其进行了表征。固态结构表明，配体以螯合结合模式起作用，其中两个化合物中的八元螯合环均采用扭转舟构象。CO拉伸频率的固态IR数据与Re，（1 + / 2 +）对在1,2和三羰基，的N，N-螯合物之间的偶合的溶液相伏安测量结果的比较表明， CH2（S-tim）2配体甚至比无处不在的二吡啶基配体更强。NMR光谱研究和伏安研究的结合表明，化合物1经过自发电离形成乙腈中的Re（CO）3（CH3CN）[ （S-tim）2] +}（Br-）。在极性较小且路易斯碱（配位较少）的溶剂（如 Cl2或丙酮）中不会发生电离。在CH3CN中离子化1时，在293 K处的平衡常数为4.3 x 10（-3）。发现
• A comparison of the coordination of two linkage isomers of bis(1-methylthioimidazolyl)methane to zinc salts
  作者：Joshua Nunn、Intan Zahedi、Georg Bauer、Mairi F. Haddow、S. Nadiah Abdul Halim、Adrián Pérez-Redondo、Gareth R. Owen

  DOI：10.1016/j.ica.2010.08.027

  日期：2011.1

  A structural comparison of the coordination chemistry of the two linkage isomeric forms of bis(1-methylthioimidazolyl)methane, [H2C(N-mt)(2)] (L-S), and [H2C(S-mt)(2)] (L-N) to a number of zinc complexes has been carried out. The complexes ZnX2LS and ZnX2LN (where X = Cl, Br and I) have all been prepared in good to high yields and have been characterised by spectroscopic and analytical methods. X-ray crystallography studies were also carried out on all of the newly prepared compounds, revealing kappa(2)-SS and kappa(2)-NN coordination modes for L-S and L-N containing complexes, respectively. (C) 2010 Elsevier B.V. All rights reserved.
• Anion- and Solvent-Directed Assembly in Silver Bis(thioimidazolyl)methane Chemistry and the Silver−Sulfur Interaction
  作者：Rosalice M. Silva、Mark D. Smith、James R. Gardinier

  DOI：10.1021/ic052025a

  日期：2006.3.1

  The effect of metal complexation on the structure and properties of the electroactive bis(l-methylthioimidazolyl)methane linkage isomers CH2(N-tim)(2) (L1) and CH2(S-tim)(2) (L2) has been explored. Coordination polymers [Ag(L1)(2)]X}(n) (X = BF4, PF6) are formed by bridging L1 between tetrahedral silver centers giving two-dimensional cationic sheets composed of AgS4 linkages; the anions are sandwiched between sheets. Cyclic climers [Ag-2(L2)(2)]-X-2} (X = BF4, PF6, OSO2CF3) are formed when L2:AgX ratios are lower than 1.5. When L2:AgPF6 was 1.5 or higher, the complex [Ag-4(L2)(5)](PF5)(4) could be isolated as a solvate. The NMR, IR, electrochemical, and ESI(+) mass spectral data of this latter compound indicate that extensive dissociation to the cyclic dimer and free ligand occurs in solution. Finally, a Cambridge Structural Database search was performed to provide insight into reasonable silver-sulfur bond distances, since literature values appeared to vary widely between 2.3 and 3.2 angstrom. It was found that these distances increase with increasing coordination number of silver. The average distances for 2-, 3-, 4-, 5-, and 6-coordinate silver were found to be 2.40, 2.52, 2.62, 2.70, and 2.75 angstrom, respectively.