1,3-二甲基-2-硫代甲基-3H-苯并咪唑碘化物 | 21337-32-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并咪唑类
• 中文名称: 1,3-二甲基-2-硫代甲基-3H-苯并咪唑碘化物
• 英文名称: 1,3-dimethyl-2-(methylthio)benzoimidazolium Iodide
• 英文别名: 1,3-dimethyl-2-(methylsulfanyl)-1H-1,3-benzodiazol-3-iumiodide；1,3-dimethyl-2-methylsulfanylbenzimidazol-3-ium;iodide
• CAS: 21337-32-6
• 化学式: C₁₀H₁₃N₂S*I
• 分子量: 320.197
• InChiKey: INVGEKZFFFXYSY-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  -1.27
• 重原子数：
  14.0
• 可旋转键数：
  1.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  8.81
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  1,3-二甲基-2-硫代甲基-3H-苯并咪唑碘化物 在 吡啶 作用下， 生成 1,3-二甲基苯并咪唑-2-硫酮
  参考文献：
  名称：

  Futaki, Yakugaku Zasshi/Journal of the Pharmaceutical Society of Japan, 1954, vol. 74, p. 1365,1367, 1368

  摘要：

  DOI：
• 作为产物：
  描述：

  1,3-二甲基苯并咪唑-2-硫酮 、 碘甲烷 以 乙腈 为溶剂， 以84%的产率得到1,3-二甲基-2-硫代甲基-3H-苯并咪唑碘化物
  参考文献：
  名称：

  非纯阴离子决定阳离子烷基化剂的机理

  摘要：

  合成了基于硫咪唑鎓离子液体的烷基化试剂，并通过实验和计算方法详细探讨了阴离子对烷基化反应机理的影响。硫咪唑鎓阳离子将烷基取代基转移到亲核试剂上，但是反应速率高度依赖于阴离子的同一性，表明阴离子在该机理中并非无害的。对与可能的机理相关的计算得出的势能面的详细分析表明，这种依赖性源自阴离子诱导的电子，空间和配位效应的结合，高度亲核的阴离子催化两步过程，而高度非亲核的离域阴离子倾向于第一步反应。这项工作还证实了溶液中离子对和聚集体的存在，从而支持了阴离子诱导的对反应速率和机理的控制。这些发现为旧反应提供了新的见解，从而可以在合成，基因表达，聚合物科学和蛋白质化学应用中更好地设计阳离子烷基化剂。

  DOI：

  10.1002/chem.202004208

文献信息

• Supramolecular Vesicles Coassembled from Disulfide-Linked Benzimidazolium Amphiphiles and Carboxylate-Substituted Pillar[6]arenes that Are Responsive to Five Stimuli
  作者：Long Jiang、Xuan Huang、Dong Chen、Hua Yan、Xueyuan Li、Xuezhong Du

  DOI：10.1002/anie.201611973

  日期：2017.3.1

  Novel supramolecular vesicles based on host–guest systems were coassembled from carboxylate‐substituted pillar[6]arene (CPA[6]) and disulfide‐linked benzimidazolium amphiphiles, and the microstructures of the CPA‐based supramolecular vesicles were clearly elaborated. The supramolecular vesicles showed controlled drug release in response to five stimuli, with glutathione, pH, CO2, Zn2+ ions, and hexanediamine

  基于客体-客体系统的新型超分子囊泡是由羧酸取代的柱[6]芳烃（CPA [6]）和二硫键连接的苯并咪唑两亲物共同组装而成，并且基于CPA的超分子囊泡的微观结构得到了清晰阐述。超分子囊泡对谷胱甘肽，pH，CO 2，Zn 2+的五种刺激均显示出受控的药物释放离子和己二胺，导致二硫键断裂，羧酸根的质子化，金属螯合和竞争性结合。这是基于智能的基于柱状芳烃的超分子囊泡的首例，该囊泡具有五种刺激响应功能，可以满足药物控制释放的多种要求。重要的是，这五个刺激中的每一个都与人体肿瘤和疾病的微环境密切相关。智能的刺激反应性超分子囊泡在肿瘤和相关疾病的药物治疗中具有广阔的应用前景。
• Thioimidazolium Ionic Liquids as Tunable Alkylating Agents
  作者：Ryan Guterman、Han Miao、Markus Antonietti

  DOI：10.1021/acs.joc.7b02631

  日期：2018.1.19

  the cation to profoundly affect the reactivity of these alkylating ionic liquids, with a caffeine-derived compound possessing the highest reactivity. Anion choice was found to affect reaction rates, with iodide anions assisting in the alkylation reaction through a “shuttling” process. The ability to tune the properties of the alkylating agent using the toolbox of ionic liquid chemistry highlights the

  基于硫代咪唑结构的烷基化离子液体将离子液体的常规特性（包括低熔点和不挥发性）与烷基化功能结合在一起。烷基转移仅发生于S-烷基位置，因此允许在不损害特异性的情况下使结构容易衍生。我们应用此功能来调整阳离子的亲电性，以深刻影响这些烷基化离子液体的反应性，其中咖啡因衍生的化合物具有最高的反应性。发现阴离子的选择会影响反应速率，其中碘化物阴离子通过“穿梭”过程协助烷基化反应。使用离子液体化学工具箱调节烷基化剂性能的能力突显了这些化合物的模块化性质，作为烷基化剂设计和集成到未来系统中的平台。
• Structure of rhodanine cyanine dyes, spectroscopy and performance in photographic emulsions
  作者：Zheng-Hong Peng、Xiang-Feng Zhou、Suzanne Carroll、Herman J. Geise、Bi-xian Peng、Roger Dommisse、Eddy Esmans、Robert Carleer

  DOI：10.1039/jm9960601325

  日期：——

  The synthesis is reported of eight pyridine–, benzothiazole– and benzimidazole–rhodanine zeromethine merocyanines as blue–sensitising dyes (1–8), and of three benzoxazole-rhodanine dimethine merocyanines as green-sensitising dyes (9–11). The compounds were characterised from UV–VIS, mass spectroscopic and NMR data, and the purity of the products was analysed using HPLC. Oxidation potentials were measured using cyclic voltammetry. Ionisation potentials and electron affinities were obtained by semi-empirical MOPAC calculations. The charge-density distributions of the pyridine and benzothiazole rhodanine dyes are in agreement with assignments in NMR spectroscopy. A linear dependence is found between the oxidation potential and ionisation potential, as well as between the reduction potential and electron affinity. Reflection spectra of 6 and 7 coated on photographic emulsions showed J-aggregate absorption at λ= 450 and 465 nm, respectively. The sensitising properties of the merocyanine dyes were evaluated in actual photographic T-grain emulsions.

  报告了 8 种作为蓝色敏化染料的吡啶、苯并噻唑和苯并咪唑-罗丹宁零甲胺美拉德花青素（1-8）和 3 种作为绿色敏化染料的苯并恶唑-罗丹宁二甲胺美拉德花青素（9-11）的合成。根据紫外可见光谱、质谱和核磁共振数据对这些化合物进行了表征，并使用高效液相色谱分析了产品的纯度。使用循环伏安法测量了氧化电位。电离电位和电子亲和力是通过半经验 MOPAC 计算获得的。吡啶和苯并噻唑罗丹宁染料的电荷密度分布与核磁共振光谱的分配一致。氧化电位和电离电位之间以及还原电位和电子亲和力之间呈线性关系。涂在感光乳剂上的 6 和 7 的反射光谱显示，在 λ= 450 和 465 纳米处分别有 J-聚集吸收。在实际的照相 T 粒乳剂中对梅洛菁染料的敏化特性进行了评估。
• Specific Molecular Orbital Contributions to Nucleophilicity. The Thiocarbonyl Group as Priviledged Monitor to Pinpoint Active and Less Active Molecular Orbitals in Reactions with Methylating Agents
  作者：M. Arbelot、A. Allouche、K. F. Purcell、M. Chanon

  DOI：10.1021/jo00113a010

  日期：1995.4

  The rate constants for 41 compounds bearing a C=S function reacting with MeX (X = I, Tos) span 7 orders of magnitude. The PES spectra of these compounds display two very low energy peaks, which stand clearly apart from the other peaks. These two peaks correspond to the pi orbitals of the C-S group; one is its CS pi bonding orbital oriented out of the molecular plane (pi(CS)) and the other its p-type in-plane lone pair orbital (pi(S)). For some of the compounds, the HOMO is the pi(CS) orbital and for others the HOMO is the ns lone pair orbital. The best correlation (R = 0.96) between rate constants h and PES data is obtained when In(k) is plotted against the inverse of PES energy of the pi(S) lone pair orbital. Whether this lone pair orbital is the HOMO or the next lower HOMO has no importance. A modest correlation (R = 0.78) is obtained when In(k) is plotted against the inverse of PES energy of the pi(CS) bonding orbital, An attempt to correlate the calculated energy of the third highest occupied orbital (from AM1 calculations) with In(h) provides a complete scattering of data (R < 0.1), but the calculated energy of the second lone pair orbital sigma(S) (approximate to 90 kcal mol-l deeper than the HOMO) correlates reasonably with In(h) (R = 0.88). The energies of the S 2s and 2p core orbitals (calculated for 13 cyclic compounds with the HF/3-21G technique to be 4000 to 5500 kcal mol(-1) deeper than HOMO) correlate with In(k) (R = 0.86) as well as does that of the second lone pair orbital os. These results are the first where both frontier orbitals and core orbitals display correlation with overall reactivity. They are discussed in terms of direct (perturbational) versus indirect (nonperturbational) concepts.
• 74. Anhydro-compounds from nitrogen-containing derivatives of thioglycollic acid. Part II. Glyoxaline and benziminazole compounds
  作者：G. F. Duffin、J. D. Kendall

  DOI：10.1039/jr9560000361

  日期：——