2-Methylthio-1,3-dithiolanium-iodid | 69578-60-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二硫杂环戊烷
• 英文名称: 2-Methylthio-1,3-dithiolanium-iodid
• 英文别名: 2-Methyylmercapto-<1,3>-dithiolan-carbeniumiodid；methyl(1,3-dithiolan-2-ylidene)sulfonium iodide；(1,3-dithiolan-2-yliden)methylsulfonium iodide；(1,3-Dithiolan-2-ylidene)(methyl)sulfanium iodide；1,3-dithiolan-2-ylidene(methyl)sulfanium;iodide
• CAS: 69578-60-5
• 化学式: C₄H₇S₃*I
• 分子量: 278.202
• InChiKey: VHBWTTKVMJEUQA-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  -1.73
• 重原子数：
  8
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  51.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  对硝基苯乙腈 、 2-Methylthio-1,3-dithiolanium-iodid 在 三乙胺 作用下， 以 丙醇 为溶剂， 反应 1.0h， 以50%的产率得到4-<α-(1,3-Dithiolan-2-yliden)-α-cyanomethyl>-nitrobenzen
  参考文献：
  名称：

  Fanghaenel, E.; Kuehnemund, K.-H.; Richter, A. M., Journal fur praktische Chemie (Leipzig 1954), 1988, vol. 330, # 4, p. 590 - 606

  摘要：

  DOI：
• 作为产物：
  描述：

  三硫代碳酸乙烯酯 、 碘甲烷 以 丙酮 为溶剂， 生成 2-Methylthio-1,3-dithiolanium-iodid
  参考文献：
  名称：

  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

  摘要：

  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.

  DOI：

  10.1021/jo00113a010

文献信息

• 4-(Substituted alkyl)-N-(1,3-dithiolan-2-ylidene(aniline
  申请人：Merrell Dow Pharmaceuticals Inc.

  公开号：US04391818A1

  公开（公告）日：1983-07-05

  N-(1,3-dithiolan-2-ylidene)-4-alkylanilines having a hydroxy, alkoxy or alkanoyloxy substituent on the alkyl group are useful as anti-inflammatory agents, as analgesic agents and as antiasthmatic agents. The compounds involved can be prepared by the reaction of an appropriate 4-alkylaniline with a methyl(1,3-dithiolan-2-ylidene)sulfonium salt or with carbon disulfide and ethylene dibromide in the presence of a base.

  具有烷基上羟基、烷氧基或烷酰氧基取代基的N-(1,3-二硫代环戊烷-2-基)-4-烷基苯胺可作为抗炎药、镇痛药和抗哮喘药物。所涉及的化合物可以通过将适当的4-烷基苯胺与甲基(1,3-二硫代环戊烷-2-基)亚砜盐或与碳二硫化物和溴乙烷在碱存在下反应来制备。
• Ring Expansion Reaction of Heterocyclic Cation Compounds by Incorporating One Nitrogen Atom Using I₂–NH₃System
  作者：Katsumi Yonemoto、Isao Shibuya

  DOI：10.1246/cl.1989.89

  日期：1989.1

  The reaction of various heterocyclic cation compounds with I2/NH4OH resulted in ring expansion on nitrogen atom. The similar ring expansion reaction occurred on the corresponding triiodides with NH4OH. The reaction mechanism based on initial nucleophilic attack of NH3 on cations, subsequent oxidative iodination, and liberation of I− is proposed.

  各种杂环阳离子化合物与 I2/NH4OH 的反应导致氮原子上的环膨胀。类似的扩环反应发生在相应的三碘化物与 NH4OH 上。提出了基于 NH3 对阳离子的初始亲核攻击、随后的氧化碘化和 I- 释放的反应机制。
• 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.
• Fanghaenel, E.; Kuehnemund, K.-H.; Richter, A. M., Journal fur praktische Chemie (Leipzig 1954), 1988, vol. 330, # 4, p. 590 - 606
  作者：Fanghaenel, E.、Kuehnemund, K.-H.、Richter, A. M.

  DOI：——

  日期：——