2,4,4,6-tetraphenyl-4H-thiopyran | 96271-76-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2,4,4,6-tetraphenyl-4H-thiopyran
• 英文别名: 2,4,4,6-tetraphenyl-4H-thiopyran；4H-Thiopyran, 2,4,4,6-tetraphenyl-；2,4,4,6-tetraphenylthiopyran
• CAS: 96271-76-0
• 化学式: C₂₉H₂₂S
• 分子量: 402.56
• InChiKey: DFWDUKKEEQAXFV-UHFFFAOYSA-N

物化性质

• 熔点：
  156-157 °C
• 沸点：
  582.1±50.0 °C(Predicted)
• 密度：
  1.171±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  8.1
• 重原子数：
  30
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.03
• 拓扑面积：
  25.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2,4,4,6-tetraphenyl-4H-thiopyran 在 溴 作用下， 以 二硫化碳 为溶剂， 以82%的产率得到3,5-Dibromo-2,4,4,6-tetraphenyl-4H-thiopyran
  参考文献：
  名称：

  Electrophilic 3,5-Substitution of 2,4,4,6-Tetraphenyl-4H-pyran and Some of Its 1-Heteroanalogues

  摘要：

  二溴与杂环化合物I-IV反应得到相应的3,5-二溴衍生物，而与二氯发生的选择性较低的反应只在4H-硫代吡喷IV和1,4-二氢吡啶II的情况下产生了3,5-二氯衍生物XII和可能式XIII的三氯衍生物。磷五氯化物与底物I反应得到二氯衍生物IX。化合物I-IV的硝化反应得到3,5-二硝基衍生物XV-XVIII，但也得到了一硝基衍生物XIX和XX。使用二碘对化合物II-IV进行碘化反应失败。

  DOI：

  10.1135/cccc19920546
• 作为产物：
  描述：

  2,4,4,6-tetraphenyl-4H-pyran 在 tetraphosphorus decasulfide 作用下， 以 xylene 为溶剂， 反应 36.0h， 以60%的产率得到2,4,4,6-tetraphenyl-4H-thiopyran
  参考文献：
  名称：

  新的制备和2,4,4,6-的四芳-4光致变色特性ħ -thiopyrans

  摘要：

  1,3,3,5-Tetraarylpentane -1,5-二酮2和5与tetraphosphodecasulfide反应在二甲苯中在升高的温度下，得到相应的2,4,4,6-四芳-4- ħ -thiopyrans 4和7。这种转化的机制涉及的脱水的快速初始步骤2和5至2,4,4,6-四芳-4- ħ -pyrans 3，随后较慢变换到4 ħ -噻喃类似物4。使用2D NMR技术，可以完全指定1-氧化物和1,1-二氧化物类似物的1 H和13 C NMR光谱已经进行了4（1，X = SO和SO 2）以及化合物3c，j，I，m，4a – m，6（吡喃类似物7）和7的合成。紫外线照射后，化合物4和7发生可逆的光化学颜色变化。新吸收带的最大值位于540–660 nm。4a光致脱色的非指数时间依赖性根据分散的一阶反应动力学分析了固态中的C -1。双氧加速了脱色过程；299 K的半衰期在空气中持续6600

  DOI：

  10.1039/p29920001301

文献信息

• Synthesis of Some New Functionalized 2,4,4,6-Tetraphenyl-4H-thiopyrans and Study on Their Photocolouration
  作者：Jiří Kroulík、Martin Chadim、Miroslav Polášek、Stanislav Nešpůrek、Josef Kuthan

  DOI：10.1135/cccc19980662

  日期：——

  A series of nineteen new 2,4,4,6-tetraphenyl-4H-thiopyrans both symmetrically and asymmetrically functionalized in the 3- and 5-positions of the 4H-thiopyran ring (-Br, -NO₂, -CN) and/or in the 4-positions of the 2- and 6-phenyl groups (-Br, -CN, -OMe, -CO-Ph, -COCF₃, -CO₂H) was prepared and the influence of the substituents on their photocolouration was followed. The title compounds were prepared by substitution reactions of the parent thiopyrans or by cyclization of suitably substituted 1,3,3,5-tetraarylpentane-1,5-diones. The substances lacking the 3,5-substituents exhibited blue or green UV-photocolouration while the 3- and/or 5-substituted species did not. Typical bleaching process for a selected compound is analyzed in terms of dispersive first-order kinetics.

  一系列新的对称和非对称功能化的19个2,4,4,6-四苯基-4H-硫喹啉化合物在4H-硫喹啉环的3和5位（-Br，-NO2，-CN），以及2-和6-苯基团的4位（-Br，-CN，-OMe，-CO-Ph，-COCF3，-CO2H）进行了制备，并跟踪它们的光致变色性能。这些标题化合物是通过对母硫喹啉的取代反应或对适当取代的1,3,3,5-四芳基戊二酮进行环化制备的。缺少3,5-取代基的物质表现出蓝色或绿色的紫外光致变色，而具有3和/或5-取代基的物种则不具有这种性质。对所选化合物的典型漂白过程进行了以色散一级动力学为基础的分析。
• Photochemical Transformations of 2,4,4,6-Tetraphenyl-4H-thiopyran-1,1-dioxide and Some Its para-Substituted Derivatives
  作者：Pavel Šebek、Petr Sedmera、Josef Kuthan

  DOI：10.1135/cccc19930869

  日期：——

  1,2,4,5-Tetrasubstituted cyclopentadienes VIa-VIf or phenanthrene derivative VIII, respectively, were obtained as the main photoproducts upon irradiation of sulfones Ia-If and II in acetonitrile, methanol or benzene. Bridged isomers Va-Vd were isolated from the reaction of Ia-Id carried out in acetonitrile. Probable course of the investigated photochemical transformations of 4H-thiopyran-1,1-dioxides is discussed.

  1,2,4,5-四取代环戊二烯VIa-VIf或菲喃衍生物VIII分别在乙腈、甲醇或苯中照射磺酮Ia-If和II时作为主要光产物得到。在乙腈中进行的Ia-Id反应中，分离出桥联异构体Va-Vd。讨论了4H-硫代吡喃-1,1-二氧化物的光化学转化的可能过程。
• Rearrangement of Substituted 2,4,4,6-Tetraaryl-4H-thiopyrans to Triaryl-3aH-benzo[3,4]cyclopenta[1,2-b]thiophene
  作者：Jiří Kroulík、Jan Čejka、Petr Sedmera、Alexandr Jegorov、Bohumil Kratochvíl、Josef Kuthan

  DOI：10.1135/cccc20041631

  日期：——

  An intensive bromination of 2,6-diaryl-4,4-diphenyl-4H-thiopyrans can lead through 3,5-dibromo derivatives to unexpected 2,8-diaryl-3-bromo- and 2,8-diaryl-3,5-dibromo-3a-phenyl-3aH-benzo[3,4]cyclopenta[1,2-b]thiophene as demonstrated on examples where the respective aryl groups are phenyl or 4-fluorophenyl. On the other hand, analogous spiro- [fluorene-9,4'-thiopyran]s do not exhibit the rearrangement evidently due to a rigid conformation of the fluorene moiety. The reaction mechanism for the rearrangement is proposed.

  对2,6-二芳基-4,4-二苯基-4H-硫杂环戊烷进行强烈的溴化反应，可以通过3,5-二溴衍生物导致意外的2,8-二芳基-3-溴和2,8-二芳基-3,5-二溴-3a-苯基-3aH-苯并[3,4]环戊-[1,2-b]噻吩的形成，其中所述芳基基团分别为苯基或4-氟苯基。另一方面，类似的螺[芴-9,4'-硫杂环戊烷]不表现出明显的重排反应，可能由于芴基团的刚性构象。提出了重排反应的反应机理。
• Reactions of 2,4,4,6-Tetraaryl-4H-thiopyrans with Chlorine: An Unusual Reaction Route
  作者：Pavel Šebek、Jiří Kroulík、Petr Sedmera、Vladimír Havlíček、Josef Kuthan

  DOI：10.1135/cccc19942269

  日期：——

  2,4,4,6-Tetraaryl-4H-thiopyrans Ia - Ig react smoothly with carbon disulfide solution of chlorine already at 0 °C yielding the corresponding 3,5-dichloro derivatives IIa - IIg. With longer reaction time and temperature raised to 20 °C, the 4H-thiopyrans Ia - Ie gave exclusively the trichloro derivatives IIIa - IIIe whereas If and Ig underwent a nonselective chlorination leading to multicomponent mixtures of products. Isolation of sulfoxides IVa and IVe from the chlorination of Ia and Ie (upon hydrolysis of the reaction mixture) allowed us to formulate the reaction mechanism for the formation of compounds type III. ¹H, ¹³C NMR, and mass spectra of the prepared compounds are discussed in detail.

  2,4,4,6-四芳基-4H-硫代吡喃Ia - Ig在0°C时与二硫化碳溶液中的氯反应顺利，生成相应的3,5-二氯衍生物IIa - IIg。随着反应时间的延长和温度升至20°C，4H-硫代吡喃Ia - Ie仅产生三氯衍生物IIIa - IIIe，而If和Ig经历非选择性氯化，导致多组分混合物的产生。从Ia和Ie的氯化反应（在反应混合物水解后）中分离出IVa和IVe的亚砜，使我们能够为III型化合物的形成提出反应机理。详细讨论了所制备化合物的1H、13C核磁共振和质谱。
• Photochemical reaction of 2,4,4,6-tetraaryl-4H-pyrans and -4H-thiopyrans with colour change by a 1,5-electrocyclic reaction. X-Ray molecular structure of 4-methyl-2,3,6-triphenyl-2H-thiopyran
  作者：Yukie Mori、Koko Maeda

  DOI：10.1039/p29910002061

  日期：——

  2,4,4,6-Tetraphenyl-4H-pyran and -4H-thiopyran exhibited a photochemical colour change in the solid state. On irradiation in solution, 2,4,4,6-tetraphenyl-4H-pyran gave 1,3,5,6-tetraphenyl-2-oxabicyclo[3.1.0]hex-3-ene, while the 4H-thiopyran gave 1,3,5,6-tetraphenyl-2-thiabicyclo[3.1.0]hex-3-ene as an initial photoproduct, followed by further transformation into 2,3,4,6-tetraphenyl-2H-thiopyran. 4-(4-Bromophenyl)-2,4,6-triphenyl-4H-pyran, 4-(4-methylphenyl)-2,4,6-triphenyl-4H-pyran, and 4-(4-bromophenyl)-2,4,6-triphenyl-4H-thiopyran also showed photochemical colour changes and finally gave both the phenyl-migrated and the (substituted phenyl)-migrated products in comparable yields in each case. 4-Methyl-2,4,6-triphenyl-4H-thiopyran showed no photochemical colour change in the solid state, but in solution it afforded 4-methyl-2,3,6-triphenyl-2H-thiopyran, whose structure was confirmed by X-ray analysis. Based on comparison with the photochemical behaviour of 2,4,4,6-tetraphenyl-1,4-dihydropyridine and 2,2,4,6-tetraphenyl-1,2-dihydro-1,3,5-triazine, a six-membered ylide was proposed as the coloured photochemical intermediate.