1-methyl-2,3-bis(phenylthio)indole | 63955-64-6

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: 1-methyl-2,3-bis(phenylthio)indole
• 英文别名: 1-methyl-2,3-bis(phenylthio)-1H-indole；1-Methyl-2,3-bis(phenylsulfanyl)-1H-indole；1-methyl-2,3-bis(phenylsulfanyl)indole
• CAS: 63955-64-6
• 化学式: C₂₁H₁₇NS₂
• 分子量: 347.505
• InChiKey: DPSOYDQYEVNMAH-UHFFFAOYSA-N

物化性质

• 熔点：
  107 °C
• 沸点：
  517.2±35.0 °C(Predicted)
• 密度：
  1.17±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.5
• 重原子数：
  24
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.05
• 拓扑面积：
  55.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-methyl-2,3-bis(phenylthio)indole 在 三氟乙酸 作用下， 反应 18.0h， 以86%的产率得到1-methyl-2-(phenylsulfanyl)-1H-indole
  参考文献：
  名称：

  吲哚-3-基硫化物的酸催化异构化为吲哚-2-基硫化物：重排的意想不到的分子间性质

  摘要：

  质子酸催化的吲哚-3-基硫醚（1）重排为吲哚-2-基硫醚（4），是通过分子间机理意外地进行的，该分子间机理涉及初始歧化成吲哚-2,3-二烷基二硫化物（2）和吲哚（3），然后（2）和（3）之间反应，得到重排产物（4）。

  DOI：

  10.1039/c39890000063
• 作为产物：
  描述：

  吲哚 、 alkaline earth salt of/the/ methylsulfuric acid 在 磺酰氯 、 sodium hydride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 1.33h， 生成 1-methyl-2,3-bis(phenylthio)indole
  参考文献：
  名称：

  Nonreductive Desulfenylation of 3-Indolyl Sulfides. Improved Syntheses of 2-Substituted Indoles and 2-Indolyl Sulfides

  摘要：

  Desulfenylation of 3-indolyl sulfides to the corresponding 3-unsubstituted indoles is usually carried out under reductive conditions, thus accommodating only substituents which are resistant to reduction. We have developed a nonreductive procedure for removal of a sulfide at the 3-position of indoles, using trifluoroacetic acid in the presence of a thiol as trapping agent, which is compatible with a large array of functionalities on the indole ring. In addition, the desulfenylation occurs selectively at the 3-position of the indole, and sulfide groups at other positions of the molecule remain untouched. Thus, indole 2,3-bis-sulfides are selectively desulfenylated at the 3-position, affording 3-unsubstituted 2-indolyl sulfides. This methodology broadens the use of sulfide as a protecting group for the 3-position of indoles.

  DOI：

  10.1021/jo00100a045

文献信息

• Metal Free Mono- and 2,3-Bis-sulfenylation of Indoles in Water with Sodium Sulfinates as a Sulfur Source
  作者：Changqing Liu、Jian Fan、Manyi Wu、Jiahui Chen、Yiming Zhao、Meihua Xie

  DOI：10.1002/cjoc.201800164

  日期：2018.9

  An iodine‐PPh3 mediated sulfenylation of indoles in water with stable and odorless sodium sulfinates as the sulfur source is described. The reaction could afford monosulfenylated indoles in moderate to excellent yields under metal free conditions. Moreover, double C—H sulfenylation of indoles at 2‐ and 3‐positions has also been achieved by using excess sodium sulfinates under the optimized reaction

  描述了碘-PPh 3介导的水中吲哚的亚磺酰化，以稳定无味的亚硫酸钠作为硫源。该反应可以在无金属条件下以中等至优异的产率得到单亚磺酰化的吲哚。此外，通过在优化的反应条件下使用过量的亚磺酸钠，还可以实现吲哚在2位和3位的双CH磺酰化。
• Acid-catalysed isomerization of indol-3-yl sulphides to indol-2-yl sulphides: unexpected intermolecular nature of the rearrangement
  作者：Pierre Hamel、Yves Girard、Joseph G. Atkinson

  DOI：10.1039/c39890000063

  日期：——

  The rearrangement of indol-3-yl sulphides (1) to indol-2-yl sulphides (4), catalysed by proton acids, unexpectedly proceeds by an intermolecualr mechanism involving initial disproportionation to an indole-2,3-diyl bis-sulphide (2) and an indole (3), followed by a reaction between (2) and (3) to yield the rearranged product (4).

  质子酸催化的吲哚-3-基硫醚（1）重排为吲哚-2-基硫醚（4），是通过分子间机理意外地进行的，该分子间机理涉及初始歧化成吲哚-2,3-二烷基二硫化物（2）和吲哚（3），然后（2）和（3）之间反应，得到重排产物（4）。
• Controllable Synthesis of Mono‐ and Bis‐sulfenylindoles from Indoles and Various Sulfenylation Agents Using KI/SeO ₂ System
  作者：Thewika Benchawan、Rungnapha Saeeng

  DOI：10.1002/ejoc.202200752

  日期：2022.10.13

  An efficient method for selective and controllable sulfenylation of indoles to synthesize mono- and bis-sulfenylindoles was reported by using a novel aerobic catalytic oxidation system KI/SeO2 for sulfenylation of indoles with disulfide/thiols. The method is scalable, not sensitive to moisture, and can proceed without metal catalyst.

  报道了一种有效的选择性和可控的吲哚亚磺酰化合成单和双亚磺酰吲哚的方法，该方法是使用新型好氧催化氧化系统 KI/SeO 2对二硫化物/硫醇对吲哚进行亚磺酰化。该方法具有可扩展性，对水分不敏感，并且可以在没有金属催化剂的情况下进行。
• Acid-catalyzed isomerization of 3-indolyl sulfides to 2-indolyl sulfides: first synthesis of 3-unsubstituted 2-arylthioindoles. Evidence for a complex intermolecular process
  作者：Pierre Hamel、Yves Girard、Joseph G. Atkinson

  DOI：10.1021/jo00035a029

  日期：1992.4

  The acid-catalyzed isomerization of 3-indolyl sulfides 1 to the corresponding 2-indolyl sulfides 4 provides the first synthesis of 3-unsubstituted 2-(arylthio)indoles, a hitherto unattainable class of compounds. When catalyzed by trifluoroacetic acid, the isomerization proceeds mainly via an intermolecular mechanism involving initial disproportionation to a 2,3-indolyl bis-sulfide 5 and an unsubstituted counterpart 6 followed by further interaction of these species to yield the rearranged isomer 4. A mechanism is proposed involving a role for the acid in the sulfenyl-transfer steps. This type of process also occurs, to a lesser extent, in the polyphosphoric acid catalyzed isomerization.
• HAMEL, PIERRE;GIRARD, YVES;ATKINSON, JOSEPH G., J. CHEM. SOC. CHEM. COMMUN.,(1989) N, C. 63-65
  作者：HAMEL, PIERRE、GIRARD, YVES、ATKINSON, JOSEPH G.

  DOI：——

  日期：——