2,7-Diphenyl-5H,6H,7H-imidazole[2,1-b]-1,4-thiazolium-3-thiolate | 150928-59-9

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 2,7-Diphenyl-5H,6H,7H-imidazole[2,1-b]-1,4-thiazolium-3-thiolate
• 英文别名: 2,7-Diphenyl-5,6-dihydroimidazo[2,1-b][1,3]thiazol-4-ium-3-olate
• CAS: 150928-59-9
• 化学式: C₁₇H₁₄N₂OS
• 分子量: 294.377
• InChiKey: AWVWWOSOYJAQGW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  21
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  58.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  异氰酸对硝基苯 、 2,7-Diphenyl-5H,6H,7H-imidazole[2,1-b]-1,4-thiazolium-3-thiolate 以 二氯甲烷 为溶剂， 以18%的产率得到3,8-diphenyl-1-(4-nitrophenyl)-4-oxoimidazo[1,2-a]pyrimidin-5-ylium-2-olate
  参考文献：
  名称：

  Thionation of Mesoionics with Isothiocyanates: Evidence Supporting a Four-Step Domino Process and Ruling Out a [2 + 2] Mechanism

  摘要：

  Mesoionic heterocycles derived from 1,3-thiazolium-4-olates (thioisomunchnones) undergo thionation with aryl isothiocyanates to afford the corresponding 4-thiolate derivatives. Here, we document this transformation in detail, giving a crystallographic characterization of the solid-state structures. From the mechanistic viewpoint, the formal thionation process could be consistent with a [2 + 2] reaction of the exocyclic C-O bond of the thioisomunchnone with the C=S double bond of the isothiocyanate moiety, which would be competing with a (3 + 2) process as usual in mesoionic rings. Theoretical computations at the [B3LYP/6-31G(d):PM3] level, in which only bond-forming and bond-breaking reactions and neighboring atoms are treated at the DFT level, do reproduce the experimental results and rule out the expected pathway. Calculations instead suggest the existence of a four-step domino pathway through several polar intermediates that agrees with the electronic nature of the substituents involved. The mechanistic hypothesis has further been corroborated by an experiment with isotopically C-13-labeled PhNCS that unambiguously shows the way in which the exchange reaction occurs.

  DOI：

  10.1021/jo900028c
• 作为产物：
  描述：

  1-phenylimidazolidine-2-thione 在 乙酸酐 、 三乙胺 作用下， 以 苯 为溶剂， 生成 2,7-Diphenyl-5H,6H,7H-imidazole[2,1-b]-1,4-thiazolium-3-thiolate
  参考文献：
  名称：

  通过1,3-偶极环加成的咪唑并[2,1 - b ]噻唑鎓4-油酸酯体系与芳族醛的非对映选择性合成手性噻兰

  摘要：

  咪唑并[1,2 - b ]噻唑-4-油酸酯体系与芳香族醛的区域专一性和非对映选择性的1,3-偶极环加成反应生成噻烷，然后将其热分解为烯烃。

  DOI：

  10.1016/s0040-4039(00)60505-1

文献信息

• Three- and Four-Membered Rings from Cycloadditions of 1,3-Thiazolium-4-olates and Aldehydes
  作者：Martín Avalos、Reyes Babiano、Pedro Cintas、Michael B. Hursthouse、José L. Jiménez、Mark E. Light、Ignacio López、Juan C. Palacios、Guadalupe Silvero

  DOI：10.1002/1521-3765(20010716)7:14<3033::aid-chem3033>3.0.co;2-f

  日期：2001.7.16

  cascade reaction that produces episulfides (thiiranes) or beta-lactams (2-azetidinones). This sequence is initiated by a [3+2] dipolar cycloaddition followed by ring opening of cycloadducts and intramolecular rearrangement to afford these unusual ring contractions. The nature of the reaction products depends on the structural characteristics of the starting dipole and the experimental conditions. Episulfides

  2-Aminothioisomünchnones是一种众所周知的被屏蔽的偶极子系列，在多米诺级联反应中与芳族醛发生反应，从而产生环硫化物（硫杂环丁烷）或β-内酰胺（2-氮杂环丁酮）。该序列由[3 + 2]偶极环加成反应开始，接着是环加合物的开环和分子内重排，以提供这些异常的环收缩。反应产物的性质取决于起始偶极的结构特征和实验条件。相对于两个芳基，环硫化物选择性地作为顺式异构体获得，而β-内酰胺以顺式/反式混合物形式产生。通过X射线晶体学分析明确地确定了这些结构特征。β-内酰胺仍然具有含硫的柔性无环链，生物活性环状青霉素和头孢烯的显着铅修饰。借助B3LYP / 6-31G *级别的计算，合理地优化了exo过渡结构的优先生产。
• Thionation of Mesoionics with Isothiocyanates: Evidence Supporting a Four-Step Domino Process and Ruling Out a [2 + 2] Mechanism
  作者：David Cantillo、Martín Ávalos、Reyes Babiano、Pedro Cintas、José L. Jiménez、Mark E. Light、Juan C. Palacios

  DOI：10.1021/jo900028c

  日期：2009.5.15

  Mesoionic heterocycles derived from 1,3-thiazolium-4-olates (thioisomunchnones) undergo thionation with aryl isothiocyanates to afford the corresponding 4-thiolate derivatives. Here, we document this transformation in detail, giving a crystallographic characterization of the solid-state structures. From the mechanistic viewpoint, the formal thionation process could be consistent with a [2 + 2] reaction of the exocyclic C-O bond of the thioisomunchnone with the C=S double bond of the isothiocyanate moiety, which would be competing with a (3 + 2) process as usual in mesoionic rings. Theoretical computations at the [B3LYP/6-31G(d):PM3] level, in which only bond-forming and bond-breaking reactions and neighboring atoms are treated at the DFT level, do reproduce the experimental results and rule out the expected pathway. Calculations instead suggest the existence of a four-step domino pathway through several polar intermediates that agrees with the electronic nature of the substituents involved. The mechanistic hypothesis has further been corroborated by an experiment with isotopically C-13-labeled PhNCS that unambiguously shows the way in which the exchange reaction occurs.
• Diastereoselective synthesis of chiral thiiranes by 1,3-dipolar cycloaddition of imidazo[2,1-b]thiazolium-4-olate systems with aromatic aldehydes
  作者：Pilar Areces、Martín Avalos、Reyes Babiano、Luis González、José L. Jiménez、María M. Méndez、Juan C. Palacios

  DOI：10.1016/s0040-4039(00)60505-1

  日期：1993.4

  The regiospecific and diastereoselective 1,3-dipolar cycloaddition of imidazo[1,2-b]thiazolium-4-olate systems with aromatic aldehydes gives thiiranes, which undergo thermal decomposition to olefins.

  咪唑并[1,2 - b ]噻唑-4-油酸酯体系与芳香族醛的区域专一性和非对映选择性的1,3-偶极环加成反应生成噻烷，然后将其热分解为烯烃。