trans-4-(N-phenylamino)stilbene | 410097-25-5

• 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-(N-phenylamino)stilbene
• 英文别名: 4-phenylaminostilbene；N-phenyl-4-[(E)-2-phenylethenyl]aniline
• CAS: 410097-25-5
• 化学式: C₂₀H₁₇N
• 分子量: 271.362
• InChiKey: HBTMDMMAFGLJKY-VAWYXSNFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.7
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  12
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  trans-4-(N-phenylamino)stilbene 以 四氢呋喃 、 正己烷 为溶剂， 生成 cis-4-(N-phenylamino)stilbene
  参考文献：
  名称：

  Fluorescence Enhancement of trans-4-Aminostilbene by N-Phenyl Substitutions:  The “Amino Conjugation Effect”

  摘要：

  The synthesis, structure, and photochemical behavior of the trans isomers of 4-(N-phenylamino)stilbene (1c), 4-(A methyl-N-phenylamino)stilbene (1d), 4-(NN-diphenylamino)stilbene (le), and 4-(N-(2,6dimethylphenyl)amino)stilbene (1f) are reported and compared to that of 4-aminostilbene (1a) and 4-N,N-dimethylaminostilbene (1b). Results for the corresponding 3-styrylpyridine (2) and 2-styrylnaphthalene analogues (3) are also included. The introduction of N-phenyl substituents to 4-aminostilbenes leads to a more planar ground-state geometry about the nitrogen atom, a red shift of the absorption and fluorescence spectra, and a less distorted structure with a larger charge-transfer character for the fluorescent excited state. Consequently, the N-phenyl derivatives 1c-e have low photoisomerization quantum yields and high fluorescence quantum yields at room temperature, in contrast to the behavior of la, 1b, and most unconstrained monosubstituted trans-stilbenes. The isomerization of 1c and 1d is a singlet-state process, whereas it is a triplet-state process for le, presumably due to a relatively higher singlet-state torsional barrier. The excited-state behavior of 1f resembles 1a and 1b instead of 1c-e as a consequence of the less planar amine geometry and weaker orbital interactions between the N-phenyl and the aminostilbene groups. Such an N-phenyl substituent effect is also found for 2 and 3 and thus appears to be general for stilbenoid systems. The nature of this effect can be described as an ''amino conjugation effect''.

  DOI：

  10.1021/ja016416+
• 作为产物：
  描述：

  对溴溴苄 在 tris(dibenzylideneacetone)dipalladium (0) sodium hydride 、 R-(+)-1,1'-联萘-2,2'-双二苯膦 、 sodium t-butanolate 作用下， 以 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 27.33h， 生成 trans-4-(N-phenylamino)stilbene
  参考文献：
  名称：

  Fluorescence Enhancement of trans-4-Aminostilbene by N-Phenyl Substitutions:  The “Amino Conjugation Effect”

  摘要：

  The synthesis, structure, and photochemical behavior of the trans isomers of 4-(N-phenylamino)stilbene (1c), 4-(A methyl-N-phenylamino)stilbene (1d), 4-(NN-diphenylamino)stilbene (le), and 4-(N-(2,6dimethylphenyl)amino)stilbene (1f) are reported and compared to that of 4-aminostilbene (1a) and 4-N,N-dimethylaminostilbene (1b). Results for the corresponding 3-styrylpyridine (2) and 2-styrylnaphthalene analogues (3) are also included. The introduction of N-phenyl substituents to 4-aminostilbenes leads to a more planar ground-state geometry about the nitrogen atom, a red shift of the absorption and fluorescence spectra, and a less distorted structure with a larger charge-transfer character for the fluorescent excited state. Consequently, the N-phenyl derivatives 1c-e have low photoisomerization quantum yields and high fluorescence quantum yields at room temperature, in contrast to the behavior of la, 1b, and most unconstrained monosubstituted trans-stilbenes. The isomerization of 1c and 1d is a singlet-state process, whereas it is a triplet-state process for le, presumably due to a relatively higher singlet-state torsional barrier. The excited-state behavior of 1f resembles 1a and 1b instead of 1c-e as a consequence of the less planar amine geometry and weaker orbital interactions between the N-phenyl and the aminostilbene groups. Such an N-phenyl substituent effect is also found for 2 and 3 and thus appears to be general for stilbenoid systems. The nature of this effect can be described as an ''amino conjugation effect''.

  DOI：

  10.1021/ja016416+

文献信息

• Thiyl Radical-Mediated Cleavage of Allylic C−N Bonds: Scope, Limitations, and Theoretical Support to the Mechanism
  作者：Stéphanie Escoubet、Stéphane Gastaldi、Vitaliy I. Timokhin、Michèle P. Bertrand、Didier Siri

  DOI：10.1021/ja049859x

  日期：2004.10.1

  Thiols mediate the radical isomerization of allylic amines into enamines. The reaction results in the cleavage of the allylic C-N bond, after treatment with aqueous HCl. The mechanism involves the abstraction of an allylic hydrogen alpha to nitrogen by thiyl radical, followed by a return hydrogen transfer from the thiol to the carbon gamma to nitrogen in the intermediate allylic radical. The scope and

  硫醇介导烯丙胺自由基异构化为烯胺。在用 HCl 水溶液处理后，该反应导致烯丙基 CN 键断裂。该机制涉及通过硫基自由基将氮的烯丙基氢 α 提取出来，然后将氢从硫醇返回到碳 γ 到中间烯丙基中的氮。研究了与硫醇的性质、烯丙基链的结构和氮上取代基的性质有关的反应范围和限制。实验结果的解释依据是起始烯丙胺中 C-Halpha BDE 和所得烯胺中 C-Hgamma BDE 的 DFT 计算。初始氢转移的效率是反应进行的首要条件。必须在 SH BDE 和上述两种 CH BDE 之间找到平衡。通过对起始烯丙基胺的优化几何形状进行的 NBO 计算来分析立体电子因素的发生率。为了通过 p-TolS(*) 从烯丙基和异戊二烯衍生物中提取 Halpha，进行了过渡结构的额外计算和随后的反应曲线追踪。后者使我们能够估计硫自由基从 N-异戊二烯胺和 N-烯丙胺中提取氢的速率常数。通过对起始烯丙基胺的优化几何形状进行的
• Diene-based rubber/inorganic compound complexes, methods for producing the same and rubber compositions containing the same
  申请人：JSR Corporation

  公开号：EP1215226A2

  公开（公告）日：2002-06-19

  The object of the present invention is to provide a method for producing a diene-based rubber/inorganic compound complex capable of allowing a silicic acid compound including silica and the like to be dispersed uniformly and allowing a reinforcing effect to be exerted sufficiently, as well as a complex produced by said method and a rubber composition containing said complex. A latex comprising a diene-based rubber such as styrene-butadiene copolymeric rubber, butadienestyrene-isoprene copolymeric rubber and the like is mixed with an aqueous solution of a silicate in which an alkaline salt of silicic acid such as sodium silicate, potassium silicate and the like is dissolved, and then the resultant mixture is further mixed with an aqueous solution of electrolytes containing [1] a cationic substance which has an affinity to the diene-based rubber including a cationic polymer coagulating agent such as poly(meth)acrylic ester or the like and a cationic surfactant such as alkylamine acetate or the like and [2] a salt of an acid such as hydrochloric acid, nitric acid and the like with a multivalent metal such as calcium, magnesium and the like, to form a co-coagulated material, which is followed by a drying, whereby obtaining a diene-based rubber/inorganic compound complex.

  本发明的目的是提供一种生产二烯基橡胶/无机化合物复合物的方法，该复合物能使包括二氧化硅等在内的硅酸化合物均匀分散，并能充分发挥补强效果，同时还提供一种用上述方法生产的复合物和一种含有上述复合物的橡胶组合物。将包含二烯基橡胶（如苯乙烯-丁二烯共聚橡胶、丁二烯-异戊二烯共聚橡胶等）的胶乳与硅酸盐水溶液混合，硅酸盐水溶液中溶解有硅酸钠、硅酸钾等硅酸的碱性盐、然后将所得混合物与电解质水溶液进一步混合，电解质水溶液中含有 [1] 与二烯基橡胶有亲和力的阳离子物质，包括阳离子聚合物凝固剂，如聚（甲基）丙烯酸酯或类似物和阳离子表面活性剂，如乙酸烷基胺或类似物，以及 [2] 酸盐，如盐酸、硝酸等酸的盐与钙、镁等多价金属形成共凝物，然后进行干燥，从而得到二烯基橡胶/无机化合物复合物。
• DIENE RUBBER/INORGANIC COMPOUND COMPOSITE AND METHOD FOR PRODUCING THE SAME AND RUBBER COMPOSITION
  申请人：JSR Corporation

  公开号：EP1323775A1

  公开（公告）日：2003-07-02

  The invention provides a diene-based rubber-inorganic compound composite material comprising a diene-based rubber and at least one inorganic compound selected from silica and a compound represented by the following formula (I):         wM·xSiOy·zH2O     (I) (wherein M is at least one metal selected from the group consisting of Al, Mg, Ti and Ca or a metal oxide thereof or a metal hydroxide thereof, and w is a number of 1-5, x is a number of 0-10, y is a number of 2-5 and z is a number of 0-10), and a rubber composition comprising the composite material and a crosslinking agent.

  本发明提供了一种二烯基橡胶-无机化合物复合材料，包括二烯基橡胶和至少一种选自白炭黑的无机化合物以及下式（I）所代表的化合物： wM-xSiOy-zH2O (I) (其中，M 是选自 Al、Mg、Ti 和 Ca 组成的组中的至少一种金属或其金属氧化物或其金属氢氧化物，w 是 1-5 的数字，x 是 0-10 的数字，y 是 2-5 的数字，z 是 0-10 的数字），以及包含该复合材料和交联剂的橡胶组合物。
• DIENE RUBBER/INORGANIC COMPOUND COMPOSITE AND PROCESS FOR PRODUCING THE SAME
  申请人：JSR Corporation

  公开号：EP1500679A1

  公开（公告）日：2005-01-26

  An objective of the present invention is to provide a production process capable of improving an operation efficiency of a diene-based rubber-inorganic compound composite during production by forming a composite having high dispersibility of an inorganic compound in a diene-based rubber and having relatively large crumb diameter upon coagulation. The present invention provides a process for producing a composite comprising a diene-based rubber and an inorganic compound represented by the general formula: wM · xSiOy · zH2O (where M is at least one metal element selected from the group consisting of Al, Mg, Ti and Ca, metal oxide thereof or metal hydroxide thereof, and w, x, y, and z are an integer of from 1 to 5, an integer of from 0 to 10, an integer of from 2 to 5, and an integer of from 0 to 10, respectively.), and comprises a step of mixing the inorganic compound and/or a material capable of forming the inorganic compound, an anionic compound and a dispersion liquid of the diene-based rubber.

  本发明的目的是提供一种生产工艺，通过形成一种无机化合物在二烯基橡胶中具有高分散性的复合材料，并在凝固后具有相对较大的胶粒直径，从而提高二烯基橡胶-无机化合物复合材料在生产过程中的操作效率。本发明提供了一种复合材料的生产工艺，该复合材料包括二烯基橡胶和无机化合物，其通式为：wM - xSiOy - zH2O（其中 M 至少为一种选自 Al、Mg、Ti 和 Ca 组成的组中的金属元素、其金属氧化物或其金属氢氧化物，w、x、y 和 z 分别为 1 至 5 的整数、0 至 10 的整数、2 至 5 的整数和 0 至 10 的整数），该工艺包括以下步骤：将二烯基橡胶和无机化合物混合在一起，然后将二烯基橡胶和无机化合物混合在一起，然后将二烯基橡胶和无机化合物混合在一起，然后将二烯基橡胶和无机化合物混合在一起。)，并包括将无机化合物和/或能够形成无机化合物的材料、阴离子化合物和二烯基橡胶的分散液混合的步骤。
• Organic lectroluminescent element
  申请人：IDEMITSU KOSAN COMPANY LIMITED

  公开号：EP1775335A2

  公开（公告）日：2007-04-18

  Materials for organic electroluminescence devices and organic electroluminescence devices which exhibit high efficiency of light emission and have a long life and excellent heat resistance, novel compounds and processes for producing the materials for organic electroluminescence devices are provided. The material for organic electroluminescence devices is represented by following general formula [1]: wherein A represents a substituted or unsubstituted arylene group having 22 to 60 carbon atoms, X1 to X4 each independently represent a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, X1 and X2 may be bonded to each other, X3 and X4 may be bonded to each other, Y1 to Y4 each independently represent an organic group represented by general formula [2], a to d each represent an integer of 0 to 2 and, when the arylene group represented by A has 26 or less carbon atoms, a+b+c+d>0 and the arylene group does not contain two or more anthracene nucleus; general formula [2] being: wherein R1 to R4 each independently represent hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, cyano group or form a triple bond by a linkage of R1 and R2 or R3 and R4, Z represents a substituted or unsubstituted aryl group having 6 to 20 carbon atoms and n represents 0 or 1.

  本发明提供了有机电致发光器件材料和有机电致发光器件，这些材料和器件发光效率高、寿命长、耐热性能优异，还提供了新型化合物和生产有机电致发光器件材料的工艺。 有机电致发光器件材料由以下通式[1]表示： 其中 A 代表具有 22 至 60 个碳原子的取代或未取代芳基，X1 至 X4 各自独立地代表具有 6 至 30 个碳原子的取代或未取代芳基，X1 和 X2 可以相互键合，X3 和 X4 可以相互键合、Y1至Y4各自独立地代表通式[2]所代表的有机基团，a至d各自代表0至2的整数，当A所代表的芳烯基团具有26个或更少的碳原子时，a+b+c+d>0，且芳烯基团不包含两个或更多的蒽核； 通式[2]为 其中 R1 至 R4 各自独立地代表氢原子、具有 1 至 20 个碳原子的取代或未取代的烷基、具有 6 至 20 个碳原子的取代或未取代的芳基、氰基或通过 R1 和 R2 或 R3 和 R4 的连接形成三键，Z 代表具有 6 至 20 个碳原子的取代或未取代的芳基，n 代表 0 或 1。