2,4,4,6-tetraphenyl-4H-pyran | 23800-58-0

• 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-pyran
• 英文别名: 2,4,4,6-tetraphenylpyran
• CAS: 23800-58-0
• 化学式: C₂₉H₂₂O
• 分子量: 386.493
• InChiKey: ZLIWRKPNGDBCKV-UHFFFAOYSA-N

物化性质

• 熔点：
  157-158 °C
• 沸点：
  572.7±50.0 °C(Predicted)
• 密度：
  1.152±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  7.6
• 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：
  9.2
• 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-pyran 在 tetraphosphorus decasulfide 作用下， 以 乙醇 、 xylene 为溶剂， 反应 36.08h， 生成 2H-噻喃,2,3,4,6-四苯基-
  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
• 作为产物：
  描述：

  苯乙酮 在 乙醚 、 phosphorus pentoxide 、 sodium amide 、 xylene 作用下， 生成 2,4,4,6-tetraphenyl-4H-pyran
  参考文献：
  名称：

  Peres de Carvalho, Annales de Chimie (Cachan, France), 1935, vol. <11> 4, p. 449,503

  摘要：

  DOI：

文献信息

• Conformation Dependent Cyclizations of 1,3,3,5-Tetraphenylpentane-1,5-dione
  作者：Pavel Šebek、Jiří Novotný、Bohumil Kratochvíl、Marián Schwarz、Josef Kuthan

  DOI：10.1135/cccc19922383

  日期：——

  The molecular and crystal structure of 1,3,3,5-tetraphenylpentane-1,5-dione (I) obtained from direct methods and anisotropically refined by the least-squares method shows that the two 3,3-phenyl groups force the molecule into a conformation suitable for formation of cyclic products and intermediates. Compound I crystallizes in P1 group with lattice parameters a = 8.444(1), b = 10.195(2), c = 14.618(2) Å, α = 75.52(2)°, β = 73.22(1)°, γ = 65.47(1)°. Photochemically and thermally found was the system I ↔ II. The reaction of 1,5-dione I with phenylmagnesium bromide gives the 2,3-dihydropyran derivative III, whereas complex hydrides give a mixture of IV and VI. On treatment with magnesium, the diketone I gives diol VIII. Chlorine (Cl₂) reacts with compound I to give the mono-, di-, and tetrachloro derivatives XII, XIII, and XIV, respectively. Bromine (Br₂) produces 3,5-dibromo-4H-pyran derivative XVIII, whereas I₂ only catalyzes the formation of 4H-pyran V. The formylation of dione I with dimethylformamide and POCl₃ gives the 4H-pyran-3-carbaldehyde XX. Probable mechanisms of the reactions investigated and the stereochemistry of compounds VI, VIII, XIII, and XIV are discussed.

  1,3,3,5-四苯基戊二酮（I）的分子和晶体结构是通过直接方法获得的，并通过最小二乘法进行各向异性精修，结果显示两个3,3-苯基团迫使分子呈适合形成环状产物和中间体的构象。化合物I以P1群结晶，晶格参数a = 8.444(1) Å，b = 10.195(2) Å，c = 14.618(2) Å，α = 75.52(2)°，β = 73.22(1)°，γ = 65.47(1)°。光化学和热化学发现了体系I↔II。1,5-二酮I与溴化苄镁反应得到2,3-二氢吡喃衍生物III，而复杂的氢化物给出混合物IV和VI。经镁处理，二酮I生成二醇VIII。氯气（Cl2）与化合物I反应得到单氯、二氯和四氯衍生物XII、XIII和XIV。溴气（Br2）产生3,5-二溴-4H-吡喃衍生物XVIII，而I2仅催化4H-吡喃V的形成。用二甲基甲酰胺和POCl3对二酮I进行甲酰化反应得到4H-吡喃-3-甲醛XX。讨论了所研究反应的可能机理以及化合物VI、VIII、XIII和XIV的立体化学。
• Electrophilic 3,5-Substitution of 2,4,4,6-Tetraphenyl-4H-pyran and Some of Its 1-Heteroanalogues
  作者：Marián Schwarz、Pavel Šebek、Josef Kuthan

  DOI：10.1135/cccc19920546

  日期：——

  The reaction of dibromine with the heterocycles I-IV gives corresponding 3,5-dibromo derivatives, while the less selective reactions with dichlorine afforded 3,5-dichloro derivative XII only in the case of 4H-thiopyran IV and trichloro derivative of the probable formula XIII in the case of 1,4-dihydropyridine II. Dichloro derivative IX was obtained on reaction of phosphorus pentachloride with substrate I. Nitration of compounds I-IV gives 3,5-dinitroderivatives XV-XVIII, but mononitro derivatives XIX and XX were also obtained. Iodination of compounds II-IV with di-iodine was unsuccessful.

  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。
• 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.
• Kroulik, Jiri; Cejka, Jan; Boehm, Stanislav, Journal of the Chemical Society. Perkin Transactions 2 (2001), 2002, # 11, p. 1909 - 1916
  作者：Kroulik, Jiri、Cejka, Jan、Boehm, Stanislav、Sebek, Pavel、Nespurek, Stanislav、Koshets, Igor、Sedmera, Petr、Halada, Petr、Havlicek, Vladimir、Kratochvil, Bohumil、Kuthan, Josef

  DOI：——

  日期：——
• Schwarz, Marian; Trska, Petr; Kuthan, Josef, Collection of Czechoslovak Chemical Communications, 1989, vol. 54, # 7, p. 1854 - 1869
  作者：Schwarz, Marian、Trska, Petr、Kuthan, Josef

  DOI：——

  日期：——