1,3,3,5-tetraphenylpentane-1,5-dione | 58338-00-4

• 分子结构分类: 有机化合物 - 木脂素、新木脂素和相关化合物
• 英文名称: 1,3,3,5-tetraphenylpentane-1,5-dione
• 英文别名: 1,5-Pentanedione, 1,3,3,5-tetraphenyl-
• CAS: 58338-00-4
• 化学式: C₂₉H₂₄O₂
• 分子量: 404.508
• InChiKey: MDFCEBWWORIYES-UHFFFAOYSA-N

物化性质

• 熔点：
  182-183 °C(Solv: benzene (71-43-2); ligroine (8032-32-4))
• 沸点：
  597.0±50.0 °C(Predicted)
• 密度：
  1.140±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.3
• 重原子数：
  31
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1,3,3,5-tetraphenylpentane-1,5-dione 生成 beta-苯基-查耳酮
  参考文献：
  名称：

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

  摘要：

  DOI：
• 作为产物：
  描述：

  2,4,4,6-tetraphenyl-4H-pyran 、 水 生成 1,3,3,5-tetraphenylpentane-1,5-dione
  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

• Catalyse heterogene par des sels et sans solvant
  作者：J. Boyer、R.J.P. Corriu、R. Perz、C. Reye

  DOI：10.1016/s0022-328x(00)83481-6

  日期：1980.1

  Addition with α,β unsaturated carbonyl compounds gives 1,5 dicarbonyl products. This method is very convenient and the compounds obtained can easily be separated. We assume that the role of the salt in these reactions is to activate the silicon atom by anionic coordination to form a pentacoordinated silicon intermediate.

  甲硅烷基烯醇醚与羰基化合物的反应通过非均相催化而活化。氟化铯是最好的催化剂。不饱和酮是通过使硅烷基烯醇醚与醛和酮缩合反应直接获得的。1,4与α，β不饱和羰基化合物加成，得到1,5二羰基产物。该方法非常方便，并且可以容易地分离得到的化合物。我们假设盐在这些反应中的作用是通过阴离子配位活化硅原子以形成五配位的硅中间体。
• Novel preparation and photochromic properties of 2,4,4,6-tetraaryl-4H-thiopyrans
  作者：Pavel Šbebek、Stanislav Nešpůrek、Richard Hrabal、Mojmír Adamec、Josef Kuthan

  DOI：10.1039/p29920001301

  日期：——

  compounds 3c, j, I, m, 4a–m, 6(the pyran analogue of 7) and 7 has been carried out. Compounds 4 and 7 undergo a reversible photochemical colour change after UV illumination. The maxima of the new absorption bands are situated at 540–660 nm. The non-exponential time dependence of the photodecolouration of 4a in the solid state is analysed in terms of dispersive first-order reaction kinetics. Dioxygen accelerates

  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
• 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。
• Photocolouration of 2,4,4,6-Tetraaryl-1,4-dihydropyridines: A Semiempirical Quantum Chemical Study
  作者：Stanislav Böhm、Michal Hocek、Stanislav Nešpůrek、Josef Kuthan

  DOI：10.1135/cccc19940262

  日期：——

  Molecular geometries of 1,4-dihydropyridines Ia, Ib and their possible photoisomers IIa - Va and IIb - Vb were optimized by the PM3 method. The electronic absorption spectra were calculated by the CNDO/S-CI procedure and compared with the experimental spectroscopic data. A probable mechanism of the photocolouration of Ia, Ib, caused by sunlight or UV illumination, is proposed, and structures IIIa, IIIb are assigned to violet or green coloured species.

  1,4-二氢吡啶的分子几何构型Ia，Ib及其可能的光异构体IIa-Va和IIb-Vb通过PM3方法进行了优化。利用CNDO/S-CI程序计算了电子吸收光谱，并将其与实验光谱数据进行了比较。提出了一种可能的Ia，Ib的光致变色机理，由阳光或紫外线照射引起，结构IIIa，IIIb被赋予紫色或绿色的物种。
• 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：——