trans-4,4'-tert-butylvinylstilbene | 183051-50-5

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: trans-4,4'-tert-butylvinylstilbene
• 英文别名: 4,4'-vinyl-tert-butyl-stilbene；4-(4'-tert-butylstyryl)styrene；4-(4-tert-butylstyryl)styrene；1-tert-butyl-4-[(E)-2-(4-ethenylphenyl)ethenyl]benzene
• CAS: 183051-50-5
• 化学式: C₂₀H₂₂
• 分子量: 262.395
• InChiKey: PESDBBZNDNEWBI-ZHACJKMWSA-N

物化性质

• 沸点：
  379.7±27.0 °C(Predicted)
• 密度：
  0.989±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.6
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  2-bromo-6-(hexyloxy)naphthalene 、 trans-4,4'-tert-butylvinylstilbene 在 palladium diacetate 四丁基溴化铵 、 potassium carbonate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 60.0h， 以73%的产率得到2-hexyloxy-6-(4-(4'-tert-butylstyryl)styryl)naphthalene
  参考文献：
  名称：

  Glass-Forming Binaphthyl Chromophores

  摘要：

  The use of the binaphthyl framework to synthesize glass-forming organic chromophores is described. Suzuki coupling reactions of racemic 6,6 ' -dibromo-2,2 ' -dialkoxy-1,1 ' -binaphthyl with 1,1-diphenyl-2-(4-dihydroxyboron-phenyl-)-ethene using [Pd(dppf)Cl-2] (dppf = 1,1 ' -bis(diphenylphosphino)ferrocene-) as the catalyst provide a set of chromophores with the 4-(2,2 ' -diphenyl-vinyl)-1-phenyl group at the 6- and 6 ' -positions and a range of groups on the oxygen atom. Starting with enantiomerically enriched (R)-6,6 ' -dibromo-2,2 ' -dihexyloxy-1,1 ' -binaphthyl ((R)-2Hex), one can obtain (R)-3Hex. Heck coupling reactions of 6,6 ' -dibromo-2,2 ' -dialkoxy-1,1 ' -binaphthyl compounds with styrene provide chromophores of the ty pe 2,2 ' -dialkoxy-1,1 ' -binaphthyl-6,6 ' -bis(2-phenyl-vinyl). Starting with enantiomerically enriched (R)-2Hex, one obtains (R)-4Hex. Molecules of the type 4 contain two 1-naphthyl-2-phenyl ethylene chromophores with a pseudo-orthogonal relationship. Similar procedures can be used to obtain fragments with more extended conjugation length. Thus, the Heck coupling reaction of 2Hex with 4-(4 ' -tert-butylstyryl)styrene, 1-(4 ' -tert-butylstyryl)-4-(4 ' -vinylstyryl)benzene, and 1-(3 ' ,5 ' -dihexyloxystyryl)4-(4 ' -vinylstyryl)benzene provides 5Hex, 6Hex, and 7Hex, respectively. DSC measurements and powder diffraction experiments indicate that the bi-naphthol chromophores show a resistance to crystallization. In some cases, considerably different thermal behavior is observed between enantiomerically enriched samples and their racemic counterparts. Increasing the size of the conjugated fragment on the binaphthol core leads to materials with higher glass-transition temperatures and a less pronounced tendency to crystallize. Fluorescence spectroscopy gives evidence of "excimer"-type interactions in the solid state, except for the chromophores with 4-(2,2 ' -diphenylvinyl)-1-phenyl groups. It is possible to obtain amorphous films of these chromophores directly from solution, and to fabricate light-emitting diodes, in which the electroluminescent layer corresponds to the binaphthyl chromophore.

  DOI：

  10.1002/1521-3765(20011015)7:20<4500::aid-chem4500>3.0.co;2-v
• 作为产物：
  描述：

  对叔丁基苯甲醛 在 碘 、 sodium hydride 作用下， 以 四氢呋喃 、 苯 为溶剂， 反应 24.0h， 生成 trans-4,4'-tert-butylvinylstilbene
  参考文献：
  名称：

  Oligophenylenevinylene Phane Dimers:  Probing the Effect of Contact Site on the Optical Properties of Bichromophoric Pairs

  摘要：

  Paracyclophane derivatives have been prepared that may be considered models of bichromophoric contacts in the solid. The optical properties of these compounds give insight into how bringing two chromophores into close proximity affects the photophysics of the pair. Thus, reaction of 4,7,12, 15-tetrabromo[2.2]-paracyclophane (4,7,12,15-Br4Pc) with excess 4-tert-butylstyrene using Pd(OAc)(2) under phase transfer conditions affords 4,7,12,15-tetra(4-tert-butylstyryl)[2.2]paracyclophane (3R(D)). The connectivity of 3R(D) models a contact between two distyrylbenzene molecules across the central ring. Reaction of 4,7,12,15-Br4Pc with 4-(4-tert-butylstyryl)styrene (TBSS) under similar conditions gives 4,7,12,15-tetra(4-(4'-tert-butylstyryl)styrl)[2.2]-paracyclophane (5R(D)). In 5R(D) two oligophenylenevinylene units containing five phenyl rings are connected via their central ring. Similar reaction protocols gave 2,5-dimethyl-1,4-di(4-tert-butylstyryl)benzene (3R) and 2.5-dimethyl-1,4-bis[4-(4'-tert-butylstyryl)styryl]benzene (5R). Molecules 3R and 5R serve to give the optical properties of the monomeric units. Comparison against the properties of 3R and 5R shows that the absorption and emission data of 3R(D) and 5R(D) an consistent with considerable delocalization between the two subunits across the paracyclophane bridge. The observed trends in the optical properties of these compounds are analyzed using collective electronic oscillators (CEO) representing the changes induced in the electronic density matrix upon optical excitation. Comparison of the CEO of the paracyclophane dimers with the corresponding monomers using two-dimensional plots provides an efficient method for tracing the origin of the various optical and electronic transitions by identifying the underlying changes in charge densities and bond orders. The electronic description of 3R(D) and 5R(D). in which the interchromophore contact is across the central ring, is considerably different from the description of paracyclophane dimers of similar chromophores that are connected via the terminal ring. Essentially no delocalization is observed for the "termini" dimers.

  DOI：

  10.1021/ja991611y

文献信息

• Stilbenoid Dimers:  Dissection of a Paracyclophane Chromophore
  作者：Guillermo C. Bazan、Warren J. Oldham,、Rene J. Lachicotte、Sergei Tretiak、Vladimir Chernyak、Shaul Mukamel

  DOI：10.1021/ja973816h

  日期：1998.9.1

  discrete chromophore relative to a state containing the through-space delocalized paracyclophane core. Thus, 4-vinyl[2.2]paracyclophane (5) is obtained by reaction of 4-bromo[2.2]paracyclophane (3) and ethylene using Pd(OAc)2 and P(o-tol)3. Similar reactions starting with pseudo-o- or pseudo-p-dibromo[2.2]paracyclophane (4a and 4b, respectively) give the pseudo-o- and pseudo-p-divinyl products (6a and

  使用钯介导的偶联反应合成了一系列具有不同共轭长度发色团的对环芳烷衍生物。这些分子模拟主链多发色团和共轭发光聚合物（如聚对亚苯基亚乙烯基）（PPV）中的固态相互作用。它们的光学特性使我们可以深入了解相对于包含通过空间离域对环芳烷核心的状态，位于离散生色团中的光激发的能量学。因此，使用Pd(OAc) 2 和P(o-tol) 3 通过4-溴[2.2]对环烷(3)和乙烯的反应获得4-乙烯基[2.2]对环烷(5)。以拟邻或拟对二溴[2.2] 对环烷（分别为 4a 和 4b）开始的类似反应得到拟邻和假对二乙烯基产物（分别为 6a 和 6b）。使用苯乙烯代替乙烯提供苯乙烯基取代的产物。因此，4-苯乙烯基[2.2] 对环芳烷 (7) 是从 3 中获得的，而伪对和伪邻二苯乙烯基 [2.2] 对环芳烷 (1...
• Synthesis, Spectroscopy, and Morphology of Tetrastilbenoidmethanes
  作者：Warren J. Oldham、Rene J. Lachicotte、Guillermo C. Bazan

  DOI：10.1021/ja974209x

  日期：1998.4.1

  materials are currently being considered for the active component in a variety of optoelectronic devices, most notably as the emissive layer in light-emitting diodes. 1 It is generally believed that the morphology adopted by these materials plays a fundamental role in defining their bulk performance. For example, completely amorphous and ultrapure thin films appear to provide the longest device lifetimes,

  目前正在考虑将低带隙分子和聚合物有机材料用作各种光电器件中的活性组件，最显着的是作为发光二极管中的发射层。1 人们普遍认为，这些材料采用的形态在定义它们的整体性能方面起着重要作用。例如，完全非晶态和超纯薄膜似乎可以提供最长的器件寿命，同时具有最高的效率和发光亮度。2 虽然通过在高真空下升华可以获得足够纯的低分子量荧光化合物薄膜，但这些薄膜会随着时间的推移而重结晶，从而导致设备故障。3 发光聚合物材料可以设计成保持无定形，即使在高温下，但它们更难获得高纯度。4,5 此外，固态聚合物链的紧密结合会导致结晶域。6 有序聚合物区域似乎通过促进低能量非或弱发射准分子或聚集态来降低发射效率。7 最终，由于容易的能量迁移，这些低能量位点可以主导光学特性，即使存在的浓度很小。8 即使以很小的浓度存在。8 即使以很小的浓度存在。8
• Synthesis, Morphology, and Optical Properties of Tetrahedral Oligo(phenylenevinylene) Materials
  作者：Shujun Wang、Warren J. Oldham、Raymond A. Hudack,、Guillermo C. Bazan

  DOI：10.1021/ja992924w

  日期：2000.6.1

  A novel topological strategy is described for designing amorphous molecular solids suitable for optoelectronic applications. In this approach, chromophores are attached to a tetrahdral point of convergence. Stilbenoid units were covalently linked to tetraphenylmethane, tetraphenyladamantane, or tetraphenylsilane cores using palladium catalyzed coupling methodology, Thus, reaction of E(C6H5X)(4) (E = C and adamantane, X = I; E = Si, X = Br) with styrene or 4,3'-tert-butylvinylstilbene under Heck coupling conditions yields the corresponding tetrakis(stillbenyl) (E(STB)(4)) and tetrakis(4-tert-butyIstyrylstilbenyl) (E((BuSSB)-Bu-t)(4)) compounds. Similarly, reaction of 1,1-diphenyl-2-(4-dihydroxyboronphenyl)ethene or 2-(4-pinacolatoboronphenyl)-3,3-diphenylacrylonitrile with tetrakis(4-bromophenyl)methane using Suzuki coupling methodology gives tetrakis(4,4'-(2,2-diphenyl-vinyl)-1,1'-biphenyl (C(DPVBi)(4)) or tetrakis(4,4'-(3,3-diphenylacrylonitrile biphenyl)methane (C(DPAB)(4)), respectively, in good yields. Compounds with more extended conjugation can also be prepared. Thus, reaction of excess 1-(4'-tert-butylstyryl)-4-(4'-vinylstyryl)benzene with C(C6H4I)(4) provides tetrakis(4-(4'-(4"-tert-butylstyryl)styryl)stilbenyl)methane (C(4R-Bu-t)(4)) in low yield (similar to 20%). The more soluble analogue, tetrakis(4-(4'-(3",5"-di-tert-butylstyryl)stilbenyl)methane (C(4R-2(t)Bu)(4)) is prepared similarly using 1-(3',5'-di-tert-butylstyryl)-4-(4'-vinylstyryl)benzene and in better yield (similar to 80%). Alkoxy substituents can also be used to increase solubility. Tetrakis((4-(2',5'-dioctyloxy-4'-styryl)styryl)stilbenyl)methane methane, C(4R-(OC8H17)(2))(4), was prepared by treatment of C(C6H4I)(4) with excess 2,5-dioctyloxy-1-styryl-4(4'-vinylstyryl)benzene (yield similar to 73%). The simple stilbenyl-derivatives were found by DSC measurements and powder diffraction experiments to be crystalline compounds. Comparison of single-crystal X-ray diffraction data shows that C(STB)(4) and Si(STB)(4) form isomorphous crystals. The larger E((BuSSB)-Bu-t)4, C(DPVBi)(4), and C(DPAB)(4) compounds readily form amorphous glasses with elevated glass transition temperatures (T-g = 142-190 degrees C) in the absence of solvent. Extending the conjugation length of the arm leads to more stable glasses. For example, the glass transition temperature of C(4R-Bu-t)(4) was measured at 230 degrees C. Solution phase optical spectroscopic data of E((BuSSB)-Bu-t)(4) (E = C, adamantane, and Si) are characteristic of the parent distyrylbenzene chromophore. Films, however, show broad and significantly red-shifted emission spectra. In contrast, C(DPVBi)(4) gives absorption and emission spectra which are nearly identical between dilute solution phase samples and neat solid films. The emission of C(DPAB)(4) is broad and structureless, reminiscent of exciplex or excimer emission. Films of the tetramers with longer arms (C(4R-Bu-t)(4), C(4R-2(t)Bu)(4), and C(4R-(OC8H17)(2))(4)) show emission properties which are dependent on sample history. Annealing the sample at elevated temperature leads to red-shifted emission as a result of better interdigitation between the optically active fragments.
• Glass-Forming Binaphthyl Chromophores
  作者：Jacek C. Ostrowski、Raymond A. Hudack, Jr.、Matthew R. Robinson、Shujun Wang、Guillermo C. Bazan

  DOI：10.1002/1521-3765(20011015)7:20<4500::aid-chem4500>3.0.co;2-v

  日期：2001.10.15

  The use of the binaphthyl framework to synthesize glass-forming organic chromophores is described. Suzuki coupling reactions of racemic 6,6 ' -dibromo-2,2 ' -dialkoxy-1,1 ' -binaphthyl with 1,1-diphenyl-2-(4-dihydroxyboron-phenyl-)-ethene using [Pd(dppf)Cl-2] (dppf = 1,1 ' -bis(diphenylphosphino)ferrocene-) as the catalyst provide a set of chromophores with the 4-(2,2 ' -diphenyl-vinyl)-1-phenyl group at the 6- and 6 ' -positions and a range of groups on the oxygen atom. Starting with enantiomerically enriched (R)-6,6 ' -dibromo-2,2 ' -dihexyloxy-1,1 ' -binaphthyl ((R)-2Hex), one can obtain (R)-3Hex. Heck coupling reactions of 6,6 ' -dibromo-2,2 ' -dialkoxy-1,1 ' -binaphthyl compounds with styrene provide chromophores of the ty pe 2,2 ' -dialkoxy-1,1 ' -binaphthyl-6,6 ' -bis(2-phenyl-vinyl). Starting with enantiomerically enriched (R)-2Hex, one obtains (R)-4Hex. Molecules of the type 4 contain two 1-naphthyl-2-phenyl ethylene chromophores with a pseudo-orthogonal relationship. Similar procedures can be used to obtain fragments with more extended conjugation length. Thus, the Heck coupling reaction of 2Hex with 4-(4 ' -tert-butylstyryl)styrene, 1-(4 ' -tert-butylstyryl)-4-(4 ' -vinylstyryl)benzene, and 1-(3 ' ,5 ' -dihexyloxystyryl)4-(4 ' -vinylstyryl)benzene provides 5Hex, 6Hex, and 7Hex, respectively. DSC measurements and powder diffraction experiments indicate that the bi-naphthol chromophores show a resistance to crystallization. In some cases, considerably different thermal behavior is observed between enantiomerically enriched samples and their racemic counterparts. Increasing the size of the conjugated fragment on the binaphthol core leads to materials with higher glass-transition temperatures and a less pronounced tendency to crystallize. Fluorescence spectroscopy gives evidence of "excimer"-type interactions in the solid state, except for the chromophores with 4-(2,2 ' -diphenylvinyl)-1-phenyl groups. It is possible to obtain amorphous films of these chromophores directly from solution, and to fabricate light-emitting diodes, in which the electroluminescent layer corresponds to the binaphthyl chromophore.
• Oligophenylenevinylene Phane Dimers:  Probing the Effect of Contact Site on the Optical Properties of Bichromophoric Pairs
  作者：Shujun Wang、Guillermo C. Bazan、Sergei Tretiak、Shaul Mukamel

  DOI：10.1021/ja991611y

  日期：2000.2.1

  Paracyclophane derivatives have been prepared that may be considered models of bichromophoric contacts in the solid. The optical properties of these compounds give insight into how bringing two chromophores into close proximity affects the photophysics of the pair. Thus, reaction of 4,7,12, 15-tetrabromo[2.2]-paracyclophane (4,7,12,15-Br4Pc) with excess 4-tert-butylstyrene using Pd(OAc)(2) under phase transfer conditions affords 4,7,12,15-tetra(4-tert-butylstyryl)[2.2]paracyclophane (3R(D)). The connectivity of 3R(D) models a contact between two distyrylbenzene molecules across the central ring. Reaction of 4,7,12,15-Br4Pc with 4-(4-tert-butylstyryl)styrene (TBSS) under similar conditions gives 4,7,12,15-tetra(4-(4'-tert-butylstyryl)styrl)[2.2]-paracyclophane (5R(D)). In 5R(D) two oligophenylenevinylene units containing five phenyl rings are connected via their central ring. Similar reaction protocols gave 2,5-dimethyl-1,4-di(4-tert-butylstyryl)benzene (3R) and 2.5-dimethyl-1,4-bis[4-(4'-tert-butylstyryl)styryl]benzene (5R). Molecules 3R and 5R serve to give the optical properties of the monomeric units. Comparison against the properties of 3R and 5R shows that the absorption and emission data of 3R(D) and 5R(D) an consistent with considerable delocalization between the two subunits across the paracyclophane bridge. The observed trends in the optical properties of these compounds are analyzed using collective electronic oscillators (CEO) representing the changes induced in the electronic density matrix upon optical excitation. Comparison of the CEO of the paracyclophane dimers with the corresponding monomers using two-dimensional plots provides an efficient method for tracing the origin of the various optical and electronic transitions by identifying the underlying changes in charge densities and bond orders. The electronic description of 3R(D) and 5R(D). in which the interchromophore contact is across the central ring, is considerably different from the description of paracyclophane dimers of similar chromophores that are connected via the terminal ring. Essentially no delocalization is observed for the "termini" dimers.