trans,trans,trans-1,6-bis(p-formylphenyl)-1,3,5-hexatriene | 89510-76-9

• 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: trans,trans,trans-1,6-bis(p-formylphenyl)-1,3,5-hexatriene
• 英文别名: (E,E,E)-1,6-di(4-formylphenyl)-1,3,5-hexatriene；1,6-Bis(4-formylphenyl)hexa-1,3,5-triene；4-[(1E,3E,5E)-6-(4-formylphenyl)hexa-1,3,5-trienyl]benzaldehyde
• CAS: 89510-76-9
• 化学式: C₂₀H₁₆O₂
• 分子量: 288.346
• InChiKey: YYZOFWPAGUWHTM-CRQXNEITSA-N

物化性质

• 沸点：
  527.9±50.0 °C(Predicted)
• 密度：
  1.156±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  22
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 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：

  trans,trans,trans-1,6-bis(p-formylphenyl)-1,3,5-hexatriene 在 碘 、 sodium ethanolate 作用下， 以 甲苯 、 苯 为溶剂， 反应 65.5h， 生成 all-trans-1,6-Bis<4-(6-phenylhexa-1,3,5-trienyl)phenyl>hexa-1,3,5-triene
  参考文献：
  名称：

  Preparation of all-trans-(1,4-phenylenehexa-1,3,5-trienylene) oligomers

  摘要：

  All-trans-(1,4-phenylenehexa-1,3,5-trienylene) oligomers, all-trans-1,4-bis(6-phenylhexa-1,3,5-trienyl)benzene (PHT2) and all-trans-1,6-bis[4-(6-phenylhexa-1,3,5-trienyl)phenyl]hexa-1,3,5-triene (PHT3), were prepared respectively by the Wittig reaction from 1,4-phenylenediacrylaldehyde or 1,6-bis[4-(2-formylvinyl)phenyl]hexa-1,3,5-triene. The H-1 NMR, IR and UV-VIS spectra of the crude oligomers indicated the presence of cis double bonds in the trienes. The cis-trans isomerization of these double bonds was carried out by heating the cis-containing crude product in an appropriate solvent with iodine catalysis. The structures of PHT2 and PHT3 were confirmed by comparison of their IR spectra with that of all-trans-1,6-diphenylhexa-1,3,5-triene.

  DOI：

  10.1039/p19930001147
• 作为产物：
  描述：

  4-(5,5-dimethyl-1,3-dioxan-2-yl)benzaldehyde 在 15-冠醚-5 、 sodium hydride 、 三氟乙酸 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 生成 trans,trans,trans-1,6-bis(p-formylphenyl)-1,3,5-hexatriene
  参考文献：
  名称：

  Synthesis and Intramolecular Electron- and Energy-Transfer Reactions of Polyyne- or Polyene-Bridged Diporphyrins

  摘要：

  A series of geometrically restricted polyyne- or polyene-bridged diporphyrins 1-7 has been prepared by a convenient, one-pot, double porphyrin cyclization reaction in acceptable yields from the corresponding dialdehydes 1-7CHO. Polyene-bridged diporphyrins 8 and 9 were prepared by a double Horner-Emmons-Wadsworth reaction of formyl-substituted zinc-porphyrin monomer 12 with bis-phosphonate esters 13 and 14, respectively. The diporphyrins 1-9 were transformed into zinc-free-base and zinc-ferric hybrid diporphyrins. Photoinduced intramolecular electron transfer in the zinc-ferric hybrid diporphyrins as well as intramolecular excitation energy transfer in the zinc-free-base hybrid diporphyrins have been studied by picosecond time-resolved fluorescence spectroscopy. Rate constants through the polyene-bridges are larger than those through the polyyne-bridges in both reactions. The distance dependence of the electron-transfer rate was found to be quite small: the attenuation factors were determined to be 0.08 and 0.1 Angstrom(-1) for the polyene- and polyyne-bridged diporphyrins, respectively. The distance dependence of the energy-transfer rate was quite similar to that of the electron transfer and was explained better by the Dexter mechanism rather than by the Forster mechanism. These results clearly demonstrate that the linear pi-conjugated polyyne and polyene spacers enhance through-bond electronic coupling between the donor and acceptor.

  DOI：

  10.1021/jo00127a024

文献信息

• A Heavy-Atom Effect on the<i>cis</i>-<i>trans</i>Photoisomerization of Bisforlmyl-Substituted<i>trans,trans,trans</i>-1,6-Diphenyl-1,3,5-hexatriene
  作者：Yoriko Sonoda、Yuji Kawanishi、Masako Sakuragi

  DOI：10.1246/cl.1999.587

  日期：1999.7

  On irradiation of p,p′-bisformyl-substituted trans,trans,trans-1,6-diphenyl-1,3,5-hexatriene in ethyl iodide, trans,trans,trans → trans,cis,trans isomerization was predominantly observed, which is in contrast to stereoselective trans,trans,trans → cis,trans,trans isomerization in common organic solvents.

  在碘化乙酯中辐照 p,p′-双甲酰基取代的反式,反式,反式-1,6-二苯基-1,3,5-己三烯时，主要观察到反式,反式,反式→反式,顺式,反式异构化，这与在普通有机溶剂中的立体选择性反式,反式,反式→顺式,反式,反式异构化不同。
• Substituent Effect on the cis-trans Photoisomerization of trans,trans,trans-1,6-Diphenyl-1,3,5-hexatrienes
  作者：Yoriko Sonoda、Hisayuki Morii、Masako Sakuragi、Yasuzo Suzuki

  DOI：10.1246/cl.1998.349

  日期：1998.4

  Quantum yield of trans,trans,trans→cis,trans,trans photoisomerization of p,p′-disubstituted 1,6-diphenyl-1,3,5-hexatriene increased as the polarity of substituents increased, regardless of their electron-withdrawing or donating nature. On the contrary, quantum yield of trans,trans,trans→trans,cis,trans isomerization increased with increasing the electron-donating nature of substituents.

  p,p'-二取代的 1,6-二苯基-1,3,5-己三烯的反式、反式、反式→顺式、反式、反式光异构化的量子产率随着取代基极性的增加而增加，无论它们的吸电子或捐赠自然。相反，反，反，反→反，顺，反异构化的量子产率随着取代基给电子性质的增加而增加。
• Intermolecular CH⋯O hydrogen bonds in formyl-substituted diphenylhexatriene, a [2+2] photoreactive organic solid: Crystal structure and IR, NMR spectroscopic evidence
  作者：Yoriko Sonoda、Midori Goto、Takuji Ikeda、Yukihiro Shimoi、Shigenobu Hayashi、Hiroshi Yamawaki、Masatoshi Kanesato

  DOI：10.1016/j.molstruc.2011.09.033

  日期：2011.12

  Abstract ( E , E , E )-1,6-di(4-formylphenyl)-1,3,5-hexatriene ( 1 ) undergoes [2 + 2] photocycloaddition in the solid state, while the unsubstituted parent, ( E , E , E )-1,6-diphenyl-1,3,5-hexatriene (DPH), is photochemically inert as we reported previously. Although the steering effect of the formyl group for the photoreaction is very clear, the crystal structure of 1 had been unknown. In this study

  摘要 ( E , E , E )-1,6-二(4-甲酰基苯基)-1,3,5-己三烯 ( 1 ) 在固态下发生 [2 + 2] 光环加成反应，而未取代的母体 ( E , E , E )-1,6-二苯基-1,3,5-己三烯 (DPH) 是光化学惰性的，正如我们之前报道的那样。虽然甲酰基对光反应的导向作用非常明确，但1的晶体结构一直未知。在这项研究中，制备了适用于 X 射线衍射 (XRD) 分析的 1 单晶并研究了晶体结构。晶体中的分子通过涉及甲酰基的分子间 CH⋯O 型氢键连接，形成 π 堆叠晶体堆积排列的 3D 结构，分子间距离为 3.926 A (= b )，小于施密特标准 4.2 A [2 + 2] 光反应。FT-IR、 1 H 和 13 C NMR 光谱测量证明了 CH⋯O 氢键的存在。对于 IR 峰分配，进行了 ab initio 和 DFT 计算。分别使用 CRAMPS 和 CP/MAS
• Solvent-Dependent<i>cis-trans</i>One-Way Photoisomerization of Bisformyl-Substituted 1,6-Diphenyl-1,3,5-hexatriene
  作者：Yoriko Sonoda、Yasuzo Suzuki

  DOI：10.1246/cl.1996.659

  日期：1996.8

  trans,trans,trans-1,6-Bis(p-formylphenyl)-1,3,5-hexatriene underwent stereoselective photoisomerization to give its cis,trans,trans isomer regardless of the solvent polarity. Quantum yields of trans,trans,trans-to-cis,trans,trans isomerization decreased dramatically with decreasing solvent polarity, whereas those of the reverse reaction gradually increased. This led to the cis,trans,trans-to-trans

  trans,trans,trans-1,6-Bis(p-formylphenyl)-1,3,5-hexatriene 进行立体选择性光异构化以得到其顺式、反式、反式异构体，而与溶剂极性无关。trans,trans,trans-to-cis,trans,trans异构化的量子产率随着溶剂极性的降低而急剧下降，而逆反应的量子产率逐渐增加。这导致了非极性溶剂中的顺式、反式、反式到反式、反式、反式“单向”异构化。
• Intermolecular [2+2] Photocycloaddition of Formyl- and Cyano-Substituted Diphenylhexatrienes in the Solid State
  作者：Yoriko Sonoda、Akira Miyazawa、Shigenobu Hayashi、Masako Sakuragi

  DOI：10.1246/cl.2001.410

  日期：2001.5

  Crystalline powder of all-trans-1,6-bis(4-R-phenyl)-1,3,5-hexatriene (R = CHO and CN) underwent intermolecular [2+2] photocycloaddition at the 1,2-position of the triene to give mirror symmetric dimers. For the formyl derivative the presence of C–H···O hydrogen bonds was suggested by IR and 13C CP/MAS NMR spectra.

  全反式-1,6-双(4-R-苯基)-1,3,5-己三烯（R = CHO和CN）的结晶粉末在三烯的1,2位发生分子间[2+2]光环加成反应，生成镜像对称二聚体。红外光谱和13C CP/MAS NMR光谱表明，甲酰衍生物中存在C–H···O氢键。